Line data Source code
1 : !--------------------------------------------------------------------------------------------------!
2 : ! CP2K: A general program to perform molecular dynamics simulations !
3 : ! Copyright 2000-2025 CP2K developers group <https://cp2k.org> !
4 : ! !
5 : ! SPDX-License-Identifier: GPL-2.0-or-later !
6 : !--------------------------------------------------------------------------------------------------!
7 :
8 : ! **************************************************************************************************
9 : !> \brief Methods for X-Ray absorption spectroscopy (XAS) using TDDFPT
10 : !> \author AB (11.2017)
11 : ! **************************************************************************************************
12 :
13 : MODULE xas_tdp_methods
14 : USE admm_types, ONLY: admm_type
15 : USE admm_utils, ONLY: admm_correct_for_eigenvalues,&
16 : admm_uncorrect_for_eigenvalues
17 : USE atomic_kind_types, ONLY: atomic_kind_type,&
18 : get_atomic_kind
19 : USE basis_set_types, ONLY: &
20 : allocate_sto_basis_set, create_gto_from_sto_basis, deallocate_gto_basis_set, &
21 : deallocate_sto_basis_set, get_gto_basis_set, gto_basis_set_type, init_orb_basis_set, &
22 : set_sto_basis_set, srules, sto_basis_set_type
23 : USE bibliography, ONLY: Bussy2021a,&
24 : cite_reference
25 : USE cell_types, ONLY: cell_type,&
26 : pbc
27 : USE cp_blacs_env, ONLY: cp_blacs_env_type
28 : USE cp_control_types, ONLY: dft_control_type
29 : USE cp_dbcsr_api, ONLY: &
30 : dbcsr_complete_redistribute, dbcsr_copy, dbcsr_create, dbcsr_filter, dbcsr_finalize, &
31 : dbcsr_get_info, dbcsr_get_occupation, dbcsr_multiply, dbcsr_p_type, dbcsr_release, &
32 : dbcsr_set, dbcsr_type, dbcsr_type_antisymmetric, dbcsr_type_no_symmetry, &
33 : dbcsr_type_symmetric
34 : USE cp_dbcsr_contrib, ONLY: dbcsr_add_on_diag
35 : USE cp_dbcsr_operations, ONLY: copy_dbcsr_to_fm,&
36 : copy_fm_to_dbcsr,&
37 : cp_dbcsr_sm_fm_multiply
38 : USE cp_files, ONLY: close_file,&
39 : open_file
40 : USE cp_fm_basic_linalg, ONLY: cp_fm_column_scale
41 : USE cp_fm_diag, ONLY: cp_fm_geeig,&
42 : cp_fm_power,&
43 : cp_fm_syevd
44 : USE cp_fm_struct, ONLY: cp_fm_struct_create,&
45 : cp_fm_struct_release,&
46 : cp_fm_struct_type
47 : USE cp_fm_types, ONLY: &
48 : cp_fm_copy_general, cp_fm_create, cp_fm_get_diag, cp_fm_get_info, cp_fm_get_submatrix, &
49 : cp_fm_read_unformatted, cp_fm_release, cp_fm_set_all, cp_fm_to_fm, cp_fm_to_fm_submat, &
50 : cp_fm_type, cp_fm_write_unformatted
51 : USE cp_log_handling, ONLY: cp_get_default_logger,&
52 : cp_logger_get_default_io_unit,&
53 : cp_logger_type,&
54 : cp_to_string
55 : USE cp_output_handling, ONLY: cp_p_file,&
56 : cp_print_key_finished_output,&
57 : cp_print_key_generate_filename,&
58 : cp_print_key_should_output,&
59 : cp_print_key_unit_nr,&
60 : debug_print_level
61 : USE input_constants, ONLY: &
62 : do_admm_purify_cauchy_subspace, do_admm_purify_mo_diag, do_admm_purify_none, do_loc_none, &
63 : do_potential_coulomb, do_potential_id, do_potential_short, do_potential_truncated, &
64 : op_loc_berry, state_loc_list, tddfpt_singlet, tddfpt_spin_cons, tddfpt_spin_flip, &
65 : tddfpt_triplet, xas_1s_type, xas_2p_type, xas_2s_type, xas_dip_len, xas_dip_vel, &
66 : xas_not_excited, xas_tdp_by_index, xas_tdp_by_kind
67 : USE input_cp2k_loc, ONLY: create_localize_section
68 : USE input_section_types, ONLY: section_release,&
69 : section_type,&
70 : section_vals_create,&
71 : section_vals_get_subs_vals,&
72 : section_vals_type,&
73 : section_vals_val_get,&
74 : section_vals_val_set
75 : USE kinds, ONLY: default_path_length,&
76 : default_string_length,&
77 : dp
78 : USE libint_wrapper, ONLY: cp_libint_static_init
79 : USE machine, ONLY: m_flush
80 : USE mathlib, ONLY: get_diag
81 : USE memory_utilities, ONLY: reallocate
82 : USE message_passing, ONLY: mp_comm_type,&
83 : mp_para_env_type
84 : USE parallel_gemm_api, ONLY: parallel_gemm
85 : USE parallel_rng_types, ONLY: UNIFORM,&
86 : rng_stream_type
87 : USE particle_methods, ONLY: get_particle_set
88 : USE particle_types, ONLY: particle_type
89 : USE periodic_table, ONLY: ptable
90 : USE physcon, ONLY: a_fine,&
91 : angstrom,&
92 : evolt
93 : USE qs_environment_types, ONLY: get_qs_env,&
94 : qs_environment_type
95 : USE qs_interactions, ONLY: init_interaction_radii_orb_basis
96 : USE qs_kind_types, ONLY: get_qs_kind,&
97 : qs_kind_type
98 : USE qs_loc_main, ONLY: qs_loc_driver
99 : USE qs_loc_methods, ONLY: centers_spreads_berry,&
100 : qs_print_cubes
101 : USE qs_loc_types, ONLY: get_qs_loc_env,&
102 : localized_wfn_control_create,&
103 : localized_wfn_control_type,&
104 : qs_loc_env_create,&
105 : qs_loc_env_release,&
106 : qs_loc_env_type
107 : USE qs_loc_utils, ONLY: qs_loc_control_init,&
108 : qs_loc_env_init,&
109 : set_loc_centers
110 : USE qs_mo_io, ONLY: write_mo_set_low
111 : USE qs_mo_methods, ONLY: calculate_subspace_eigenvalues
112 : USE qs_mo_types, ONLY: allocate_mo_set,&
113 : deallocate_mo_set,&
114 : duplicate_mo_set,&
115 : get_mo_set,&
116 : init_mo_set,&
117 : mo_set_type
118 : USE qs_operators_ao, ONLY: p_xyz_ao,&
119 : rRc_xyz_ao
120 : USE qs_pdos, ONLY: calculate_projected_dos
121 : USE qs_rho_types, ONLY: qs_rho_get,&
122 : qs_rho_type
123 : USE qs_scf_types, ONLY: ot_method_nr
124 : USE rixs_types, ONLY: rixs_env_type
125 : USE util, ONLY: get_limit,&
126 : locate,&
127 : sort_unique
128 : USE xas_methods, ONLY: calc_stogto_overlap
129 : USE xas_tdp_atom, ONLY: init_xas_atom_env,&
130 : integrate_fxc_atoms,&
131 : integrate_soc_atoms
132 : USE xas_tdp_correction, ONLY: GW2X_shift,&
133 : get_soc_splitting
134 : USE xas_tdp_integrals, ONLY: compute_ri_3c_coulomb,&
135 : compute_ri_3c_exchange,&
136 : compute_ri_coulomb2_int,&
137 : compute_ri_exchange2_int
138 : USE xas_tdp_types, ONLY: &
139 : donor_state_create, donor_state_type, free_ds_memory, free_exat_memory, &
140 : read_xas_tdp_control, set_donor_state, set_xas_tdp_env, xas_atom_env_create, &
141 : xas_atom_env_release, xas_atom_env_type, xas_tdp_control_create, xas_tdp_control_release, &
142 : xas_tdp_control_type, xas_tdp_env_create, xas_tdp_env_release, xas_tdp_env_type
143 : USE xas_tdp_utils, ONLY: include_os_soc,&
144 : include_rcs_soc,&
145 : setup_xas_tdp_prob,&
146 : solve_xas_tdp_prob
147 : USE xc_write_output, ONLY: xc_write
148 : #include "./base/base_uses.f90"
149 :
150 : IMPLICIT NONE
151 : PRIVATE
152 :
153 : CHARACTER(len=*), PARAMETER, PRIVATE :: moduleN = 'xas_tdp_methods'
154 :
155 : PUBLIC :: xas_tdp, xas_tdp_init
156 :
157 : CONTAINS
158 :
159 : ! **************************************************************************************************
160 : !> \brief Driver for XAS TDDFT calculations.
161 : !> \param qs_env the inherited qs_environment
162 : !> \param rixs_env ...
163 : !> \author AB
164 : !> \note Empty for now...
165 : ! **************************************************************************************************
166 128 : SUBROUTINE xas_tdp(qs_env, rixs_env)
167 :
168 : TYPE(qs_environment_type), POINTER :: qs_env
169 : TYPE(rixs_env_type), OPTIONAL, POINTER :: rixs_env
170 :
171 : CHARACTER(len=*), PARAMETER :: routineN = 'xas_tdp'
172 :
173 : CHARACTER(default_string_length) :: rst_filename
174 : INTEGER :: handle, n_rep, output_unit
175 : LOGICAL :: do_restart, do_rixs
176 : TYPE(section_vals_type), POINTER :: xas_tdp_section
177 :
178 64 : CALL timeset(routineN, handle)
179 :
180 : ! Logger initialization and XAS TDP banner printing
181 64 : NULLIFY (xas_tdp_section)
182 :
183 : ! check if subroutine is called as part of rixs calculation
184 64 : CALL get_qs_env(qs_env, do_rixs=do_rixs)
185 64 : IF (do_rixs) THEN
186 14 : xas_tdp_section => section_vals_get_subs_vals(qs_env%input, "PROPERTIES%RIXS%XAS_TDP")
187 : ELSE
188 50 : xas_tdp_section => section_vals_get_subs_vals(qs_env%input, "DFT%XAS_TDP")
189 : END IF
190 64 : output_unit = cp_logger_get_default_io_unit()
191 :
192 64 : IF (output_unit > 0) THEN
193 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/,T3,A,/,T3,A,/,T3,A,/)") &
194 32 : "!===========================================================================!", &
195 32 : "! XAS TDP !", &
196 32 : "! Starting TDDFPT driven X-rays absorption spectroscopy calculations !", &
197 64 : "!===========================================================================!"
198 : END IF
199 :
200 64 : CALL cite_reference(Bussy2021a)
201 :
202 : ! Check whether this is a restart calculation, i.e. is a restart file is provided
203 64 : CALL section_vals_val_get(xas_tdp_section, "RESTART_FROM_FILE", n_rep_val=n_rep)
204 :
205 64 : IF (n_rep < 1) THEN
206 : do_restart = .FALSE.
207 : ELSE
208 2 : CALL section_vals_val_get(xas_tdp_section, "RESTART_FROM_FILE", c_val=rst_filename)
209 : do_restart = .TRUE.
210 : END IF
211 :
212 : ! Restart the calculation if needed
213 : IF (do_restart) THEN
214 :
215 2 : IF (output_unit > 0) THEN
216 : WRITE (UNIT=output_unit, FMT="(/,T3,A)") &
217 1 : "# This is a RESTART calculation for PDOS and/or CUBE printing"
218 : END IF
219 :
220 2 : CALL restart_calculation(rst_filename, xas_tdp_section, qs_env)
221 :
222 : ! or run the core XAS_TDP routine if not
223 : ELSE
224 62 : IF (PRESENT(rixs_env)) THEN
225 14 : CALL xas_tdp_core(xas_tdp_section, qs_env, rixs_env)
226 : ELSE
227 48 : CALL xas_tdp_core(xas_tdp_section, qs_env)
228 : END IF
229 : END IF
230 :
231 64 : IF (output_unit > 0) THEN
232 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/,T3,A,/,T3,A,/)") &
233 32 : "!===========================================================================!", &
234 32 : "! End of TDDFPT driven X-rays absorption spectroscopy calculations !", &
235 64 : "!===========================================================================!"
236 : END IF
237 :
238 64 : CALL timestop(handle)
239 :
240 64 : END SUBROUTINE xas_tdp
241 :
242 : ! **************************************************************************************************
243 : !> \brief The core workflow of the XAS_TDP method
244 : !> \param xas_tdp_section the input values for XAS_TDP
245 : !> \param qs_env ...
246 : !> \param rixs_env ...
247 : ! **************************************************************************************************
248 62 : SUBROUTINE xas_tdp_core(xas_tdp_section, qs_env, rixs_env)
249 :
250 : TYPE(section_vals_type), POINTER :: xas_tdp_section
251 : TYPE(qs_environment_type), POINTER :: qs_env
252 : TYPE(rixs_env_type), OPTIONAL, POINTER :: rixs_env
253 :
254 : CHARACTER(LEN=default_string_length) :: kind_name
255 : INTEGER :: batch_size, bo(2), current_state_index, iat, iatom, ibatch, ikind, ispin, istate, &
256 : nbatch, nex_atom, output_unit, tmp_index
257 62 : INTEGER, ALLOCATABLE, DIMENSION(:) :: batch_atoms, ex_atoms_of_kind
258 62 : INTEGER, DIMENSION(:), POINTER :: atoms_of_kind
259 : LOGICAL :: do_os, do_rixs, end_of_batch, unique
260 : TYPE(admm_type), POINTER :: admm_env
261 62 : TYPE(atomic_kind_type), DIMENSION(:), POINTER :: atomic_kind_set
262 62 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks
263 : TYPE(dft_control_type), POINTER :: dft_control
264 : TYPE(donor_state_type), POINTER :: current_state
265 : TYPE(gto_basis_set_type), POINTER :: tmp_basis
266 62 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
267 : TYPE(xas_atom_env_type), POINTER :: xas_atom_env
268 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
269 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
270 :
271 62 : NULLIFY (xas_tdp_env, xas_tdp_control, atomic_kind_set, atoms_of_kind, current_state)
272 62 : NULLIFY (xas_atom_env, dft_control, matrix_ks, admm_env, qs_kind_set, tmp_basis)
273 :
274 : ! Initialization
275 124 : output_unit = cp_logger_get_default_io_unit()
276 :
277 62 : IF (output_unit > 0) THEN
278 : WRITE (UNIT=output_unit, FMT="(/,T3,A)") &
279 31 : "# Create and initialize the XAS_TDP environment"
280 : END IF
281 62 : CALL get_qs_env(qs_env, dft_control=dft_control, do_rixs=do_rixs)
282 62 : IF (PRESENT(rixs_env)) THEN
283 14 : CALL xas_tdp_init(xas_tdp_env, xas_tdp_control, qs_env, rixs_env)
284 : ELSE
285 48 : CALL xas_tdp_init(xas_tdp_env, xas_tdp_control, qs_env)
286 : END IF
287 62 : CALL print_info(output_unit, xas_tdp_control, qs_env)
288 :
289 62 : IF (output_unit > 0) THEN
290 31 : IF (xas_tdp_control%check_only) THEN
291 0 : CPWARN("This is a CHECK_ONLY run for donor MOs verification")
292 : END IF
293 : END IF
294 :
295 : ! Localization of the core orbitals if requested (used for better identification of donor states)
296 62 : IF (xas_tdp_control%do_loc) THEN
297 34 : IF (output_unit > 0) THEN
298 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/)") &
299 17 : "# Localizing core orbitals for better identification"
300 : END IF
301 : ! closed shell or ROKS => myspin=1
302 34 : IF (xas_tdp_control%do_uks) THEN
303 6 : DO ispin = 1, dft_control%nspins
304 : CALL qs_loc_driver(qs_env, xas_tdp_env%qs_loc_env, &
305 6 : xas_tdp_control%print_loc_subsection, myspin=ispin)
306 : END DO
307 : ELSE
308 : CALL qs_loc_driver(qs_env, xas_tdp_env%qs_loc_env, &
309 32 : xas_tdp_control%print_loc_subsection, myspin=1)
310 : END IF
311 : END IF
312 :
313 : ! Find the MO centers
314 62 : CALL find_mo_centers(xas_tdp_env, xas_tdp_control, qs_env)
315 :
316 : ! Assign lowest energy orbitals to excited atoms
317 62 : CALL assign_mos_to_ex_atoms(xas_tdp_env, xas_tdp_control, qs_env)
318 :
319 : ! Once assigned, diagonalize the MOs wrt the KS matrix in the subspace associated to each atom
320 62 : IF (xas_tdp_control%do_loc) THEN
321 34 : IF (output_unit > 0) THEN
322 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/,T5,A)") &
323 17 : "# Diagonalize localized MOs wrt the KS matrix in the subspace of each excited", &
324 34 : "atom for better donor state identification."
325 : END IF
326 34 : CALL diagonalize_assigned_mo_subset(xas_tdp_env, xas_tdp_control, qs_env)
327 : ! update MO centers
328 34 : CALL find_mo_centers(xas_tdp_env, xas_tdp_control, qs_env)
329 : END IF
330 :
331 62 : IF (output_unit > 0) THEN
332 : WRITE (UNIT=output_unit, FMT="(/,T3,A,I4,A,/)") &
333 31 : "# Assign the relevant subset of the ", xas_tdp_control%n_search, &
334 62 : " lowest energy MOs to excited atoms"
335 : END IF
336 62 : CALL write_mos_to_ex_atoms_association(xas_tdp_env, xas_tdp_control, qs_env)
337 :
338 : ! If CHECK_ONLY run, check the donor MOs
339 62 : IF (xas_tdp_control%check_only) CALL print_checks(xas_tdp_env, xas_tdp_control, qs_env)
340 :
341 : ! If not simply exact exchange, setup a xas_atom_env and compute the xc integrals on the atomic grids
342 : ! Also needed if SOC is included or XPS GW2X(). Done before looping on atoms as it's all done at once
343 : IF ((xas_tdp_control%do_xc .OR. xas_tdp_control%do_soc .OR. xas_tdp_control%do_gw2x) &
344 62 : .AND. .NOT. xas_tdp_control%check_only) THEN
345 :
346 62 : IF (output_unit > 0 .AND. xas_tdp_control%do_xc) THEN
347 : WRITE (UNIT=output_unit, FMT="(/,T3,A,I4,A)") &
348 26 : "# Integrating the xc kernel on the atomic grids ..."
349 26 : CALL m_flush(output_unit)
350 : END IF
351 :
352 62 : CALL xas_atom_env_create(xas_atom_env)
353 62 : CALL init_xas_atom_env(xas_atom_env, xas_tdp_env, xas_tdp_control, qs_env)
354 62 : do_os = xas_tdp_control%do_uks .OR. xas_tdp_control%do_roks
355 :
356 62 : IF (xas_tdp_control%do_xc .AND. (.NOT. xas_tdp_control%xps_only)) THEN
357 52 : CALL integrate_fxc_atoms(xas_tdp_env%ri_fxc, xas_atom_env, xas_tdp_control, qs_env)
358 : END IF
359 :
360 62 : IF (xas_tdp_control%do_soc .OR. xas_tdp_control%do_gw2x) THEN
361 22 : CALL integrate_soc_atoms(xas_tdp_env%orb_soc, xas_atom_env=xas_atom_env, qs_env=qs_env)
362 : END IF
363 :
364 62 : CALL xas_atom_env_release(xas_atom_env)
365 : END IF
366 :
367 : ! Compute the 3-center Coulomb integrals for the whole system
368 62 : IF ((.NOT. (xas_tdp_control%check_only .OR. xas_tdp_control%xps_only)) .AND. &
369 : (xas_tdp_control%do_xc .OR. xas_tdp_control%do_coulomb)) THEN
370 58 : IF (output_unit > 0) THEN
371 : WRITE (UNIT=output_unit, FMT="(/,T3,A,I4,A)") &
372 29 : "# Computing the RI 3-center Coulomb integrals ..."
373 29 : CALL m_flush(output_unit)
374 : END IF
375 58 : CALL compute_ri_3c_coulomb(xas_tdp_env, qs_env)
376 :
377 : END IF
378 :
379 : ! Loop over donor states for calculation
380 62 : CALL get_qs_env(qs_env=qs_env, atomic_kind_set=atomic_kind_set)
381 62 : current_state_index = 1
382 :
383 : ! Loop over atomic kinds
384 160 : DO ikind = 1, SIZE(atomic_kind_set)
385 :
386 98 : IF (xas_tdp_control%check_only) EXIT
387 136 : IF (.NOT. ANY(xas_tdp_env%ex_kind_indices == ikind)) CYCLE
388 :
389 : CALL get_atomic_kind(atomic_kind=atomic_kind_set(ikind), name=kind_name, &
390 68 : atom_list=atoms_of_kind)
391 :
392 : ! compute the RI coulomb2 inverse for this kind, and RI exchange2 if needed
393 68 : CALL compute_ri_coulomb2_int(ikind, xas_tdp_env, xas_tdp_control, qs_env)
394 68 : IF (xas_tdp_control%do_hfx) THEN
395 50 : CALL compute_ri_exchange2_int(ikind, xas_tdp_env, xas_tdp_control, qs_env)
396 : END IF
397 :
398 : !Randomly distribute excited atoms of current kinds into batches for optimal load balance
399 : !of RI 3c exchange integrals. Take batch sizes of 2 to avoid taxing memory too much, while
400 : !greatly improving load balance
401 68 : batch_size = 2
402 68 : CALL get_ri_3c_batches(ex_atoms_of_kind, nbatch, batch_size, atoms_of_kind, xas_tdp_env)
403 68 : nex_atom = SIZE(ex_atoms_of_kind)
404 :
405 : !Loop over batches
406 136 : DO ibatch = 1, nbatch
407 :
408 68 : bo = get_limit(nex_atom, nbatch, ibatch - 1)
409 68 : batch_size = bo(2) - bo(1) + 1
410 204 : ALLOCATE (batch_atoms(batch_size))
411 68 : iatom = 0
412 142 : DO iat = bo(1), bo(2)
413 74 : iatom = iatom + 1
414 142 : batch_atoms(iatom) = ex_atoms_of_kind(iat)
415 : END DO
416 68 : CALL sort_unique(batch_atoms, unique)
417 :
418 : !compute RI 3c exchange integrals on batch, if so required
419 68 : IF (xas_tdp_control%do_hfx) THEN
420 50 : IF (output_unit > 0) THEN
421 : WRITE (UNIT=output_unit, FMT="(/,T3,A,I4,A,I4,A,I1,A,A)") &
422 25 : "# Computing the RI 3-center Exchange integrals for batch ", ibatch, "(/", nbatch, ") of ", &
423 50 : batch_size, " atoms of kind: ", TRIM(kind_name)
424 25 : CALL m_flush(output_unit)
425 : END IF
426 50 : CALL compute_ri_3c_exchange(batch_atoms, xas_tdp_env, xas_tdp_control, qs_env)
427 : END IF
428 :
429 : ! Loop over atoms of batch
430 142 : DO iat = 1, batch_size
431 74 : iatom = batch_atoms(iat)
432 :
433 74 : tmp_index = locate(xas_tdp_env%ex_atom_indices, iatom)
434 :
435 : !if dipole in length rep, compute the dipole in the AO basis for this atom
436 : !if quadrupole is required, compute it there too (in length rep)
437 74 : IF (xas_tdp_control%dipole_form == xas_dip_len .OR. xas_tdp_control%do_quad) THEN
438 28 : CALL compute_lenrep_multipole(iatom, xas_tdp_env, xas_tdp_control, qs_env)
439 : END IF
440 :
441 : ! Loop over states of excited atom of kind
442 158 : DO istate = 1, SIZE(xas_tdp_env%state_types, 1)
443 :
444 84 : IF (xas_tdp_env%state_types(istate, tmp_index) == xas_not_excited) CYCLE
445 :
446 84 : current_state => xas_tdp_env%donor_states(current_state_index)
447 : CALL set_donor_state(current_state, at_index=iatom, &
448 : at_symbol=kind_name, kind_index=ikind, &
449 84 : state_type=xas_tdp_env%state_types(istate, tmp_index))
450 :
451 : ! Initial write for the donor state of interest
452 84 : IF (output_unit > 0) THEN
453 : WRITE (UNIT=output_unit, FMT="(/,T3,A,A2,A,I4,A,A,/)") &
454 42 : "# Start of calculations for donor state of type ", &
455 42 : xas_tdp_env%state_type_char(current_state%state_type), " for atom", &
456 84 : current_state%at_index, " of kind ", TRIM(current_state%at_symbol)
457 42 : CALL m_flush(output_unit)
458 : END IF
459 :
460 : ! Assign best fitting MO(s) to current core donnor state
461 84 : CALL assign_mos_to_donor_state(current_state, xas_tdp_env, xas_tdp_control, qs_env)
462 :
463 : ! Perform MO restricted Mulliken pop analysis for verification
464 84 : CALL perform_mulliken_on_donor_state(current_state, qs_env)
465 :
466 : ! GW2X correction
467 84 : IF (xas_tdp_control%do_gw2x) THEN
468 30 : CALL GW2X_shift(current_state, xas_tdp_env, xas_tdp_control, qs_env)
469 : END IF
470 :
471 : ! Do main XAS calculations here
472 84 : IF (.NOT. xas_tdp_control%xps_only) THEN
473 72 : CALL setup_xas_tdp_prob(current_state, qs_env, xas_tdp_env, xas_tdp_control)
474 :
475 72 : IF (xas_tdp_control%do_spin_cons) THEN
476 : CALL solve_xas_tdp_prob(current_state, xas_tdp_control, xas_tdp_env, qs_env, &
477 12 : ex_type=tddfpt_spin_cons)
478 12 : CALL compute_dipole_fosc(current_state, xas_tdp_control, xas_tdp_env)
479 12 : IF (xas_tdp_control%do_quad) CALL compute_quadrupole_fosc(current_state, &
480 0 : xas_tdp_control, xas_tdp_env)
481 : CALL xas_tdp_post(tddfpt_spin_cons, current_state, xas_tdp_env, &
482 12 : xas_tdp_section, qs_env)
483 12 : CALL write_donor_state_restart(tddfpt_spin_cons, current_state, xas_tdp_section, qs_env)
484 : END IF
485 :
486 72 : IF (xas_tdp_control%do_spin_flip) THEN
487 : CALL solve_xas_tdp_prob(current_state, xas_tdp_control, xas_tdp_env, qs_env, &
488 2 : ex_type=tddfpt_spin_flip)
489 : !no dipole in spin-flip (spin-forbidden)
490 : CALL xas_tdp_post(tddfpt_spin_flip, current_state, xas_tdp_env, &
491 2 : xas_tdp_section, qs_env)
492 2 : CALL write_donor_state_restart(tddfpt_spin_flip, current_state, xas_tdp_section, qs_env)
493 : END IF
494 :
495 72 : IF (xas_tdp_control%do_singlet) THEN
496 : CALL solve_xas_tdp_prob(current_state, xas_tdp_control, xas_tdp_env, qs_env, &
497 60 : ex_type=tddfpt_singlet)
498 60 : CALL compute_dipole_fosc(current_state, xas_tdp_control, xas_tdp_env)
499 60 : IF (xas_tdp_control%do_quad) CALL compute_quadrupole_fosc(current_state, &
500 0 : xas_tdp_control, xas_tdp_env)
501 : CALL xas_tdp_post(tddfpt_singlet, current_state, xas_tdp_env, &
502 60 : xas_tdp_section, qs_env)
503 60 : CALL write_donor_state_restart(tddfpt_singlet, current_state, xas_tdp_section, qs_env)
504 : END IF
505 :
506 72 : IF (xas_tdp_control%do_triplet) THEN
507 : CALL solve_xas_tdp_prob(current_state, xas_tdp_control, xas_tdp_env, qs_env, &
508 2 : ex_type=tddfpt_triplet)
509 : !no dipole for triplets by construction
510 : CALL xas_tdp_post(tddfpt_triplet, current_state, xas_tdp_env, &
511 2 : xas_tdp_section, qs_env)
512 2 : CALL write_donor_state_restart(tddfpt_triplet, current_state, xas_tdp_section, qs_env)
513 : END IF
514 :
515 : ! Include the SOC if required, only for 2p donor stataes
516 72 : IF (xas_tdp_control%do_soc .AND. current_state%state_type == xas_2p_type) THEN
517 4 : IF (xas_tdp_control%do_singlet .AND. xas_tdp_control%do_triplet) THEN
518 2 : CALL include_rcs_soc(current_state, xas_tdp_env, xas_tdp_control, qs_env)
519 : END IF
520 4 : IF (xas_tdp_control%do_spin_cons .AND. xas_tdp_control%do_spin_flip) THEN
521 2 : CALL include_os_soc(current_state, xas_tdp_env, xas_tdp_control, qs_env)
522 : END IF
523 : END IF
524 :
525 : ! Print the requested properties
526 72 : CALL print_xas_tdp_to_file(current_state, xas_tdp_env, xas_tdp_control, xas_tdp_section)
527 : END IF !xps_only
528 84 : IF (xas_tdp_control%do_gw2x) CALL print_xps(current_state, xas_tdp_env, xas_tdp_control, qs_env)
529 :
530 : ! Free some unneeded attributes of current_state
531 84 : IF (.NOT. do_rixs) CALL free_ds_memory(current_state) ! donor-state will be cleaned in rixs
532 84 : current_state_index = current_state_index + 1
533 158 : NULLIFY (current_state)
534 :
535 : END DO ! state type
536 :
537 74 : end_of_batch = .FALSE.
538 74 : IF (iat == batch_size) end_of_batch = .TRUE.
539 142 : CALL free_exat_memory(xas_tdp_env, iatom, end_of_batch)
540 : END DO ! atom of batch
541 204 : DEALLOCATE (batch_atoms)
542 : END DO !ibatch
543 228 : DEALLOCATE (ex_atoms_of_kind)
544 : END DO ! kind
545 :
546 : ! Return to ususal KS matrix
547 62 : IF (dft_control%do_admm) THEN
548 6 : CALL get_qs_env(qs_env, matrix_ks=matrix_ks, admm_env=admm_env)
549 12 : DO ispin = 1, dft_control%nspins
550 12 : CALL admm_uncorrect_for_eigenvalues(ispin, admm_env, matrix_ks(ispin)%matrix)
551 : END DO
552 : END IF
553 :
554 : ! Return to initial basis set radii
555 62 : IF (xas_tdp_control%eps_pgf > 0.0_dp) THEN
556 0 : CALL get_qs_env(qs_env, qs_kind_set=qs_kind_set)
557 0 : DO ikind = 1, SIZE(atomic_kind_set)
558 0 : CALL get_qs_kind(qs_kind_set(ikind), basis_set=tmp_basis, basis_type="ORB")
559 0 : CALL init_interaction_radii_orb_basis(tmp_basis, eps_pgf_orb=dft_control%qs_control%eps_pgf_orb)
560 : END DO
561 : END IF
562 :
563 : ! Clean-up
564 62 : IF (.NOT. do_rixs) CALL xas_tdp_env_release(xas_tdp_env) ! is released at the end of rixs
565 62 : CALL xas_tdp_control_release(xas_tdp_control)
566 :
567 124 : END SUBROUTINE xas_tdp_core
568 :
569 : ! **************************************************************************************************
570 : !> \brief Overall control and environment types initialization
571 : !> \param xas_tdp_env the environment type to initialize
572 : !> \param xas_tdp_control the control type to initialize
573 : !> \param qs_env the inherited qs environement type
574 : !> \param rixs_env ...
575 : ! **************************************************************************************************
576 62 : SUBROUTINE xas_tdp_init(xas_tdp_env, xas_tdp_control, qs_env, rixs_env)
577 :
578 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
579 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
580 : TYPE(qs_environment_type), POINTER :: qs_env
581 : TYPE(rixs_env_type), OPTIONAL, POINTER :: rixs_env
582 :
583 : CHARACTER(LEN=default_string_length) :: kind_name
584 : INTEGER :: at_ind, i, ispin, j, k, kind_ind, &
585 : n_donor_states, n_kinds, nao, &
586 : nat_of_kind, natom, nex_atoms, &
587 : nex_kinds, nmatch, nspins
588 : INTEGER, DIMENSION(2) :: homo, n_mo, n_moloc
589 62 : INTEGER, DIMENSION(:), POINTER :: ind_of_kind
590 : LOGICAL :: do_os, do_rixs, do_uks, unique
591 : REAL(dp) :: fact
592 62 : REAL(dp), DIMENSION(:), POINTER :: mo_evals
593 : TYPE(admm_type), POINTER :: admm_env
594 62 : TYPE(atomic_kind_type), DIMENSION(:), POINTER :: at_kind_set
595 : TYPE(cell_type), POINTER :: cell
596 : TYPE(cp_fm_type), POINTER :: mo_coeff
597 62 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks, matrix_s, rho_ao
598 : TYPE(dbcsr_type) :: matrix_tmp
599 : TYPE(dft_control_type), POINTER :: dft_control
600 : TYPE(gto_basis_set_type), POINTER :: tmp_basis
601 62 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
602 62 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
603 62 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
604 : TYPE(qs_loc_env_type), POINTER :: qs_loc_env
605 : TYPE(qs_rho_type), POINTER :: rho
606 : TYPE(section_type), POINTER :: dummy_section
607 : TYPE(section_vals_type), POINTER :: loc_section, xas_tdp_section
608 :
609 62 : NULLIFY (xas_tdp_section, at_kind_set, ind_of_kind, dft_control, qs_kind_set, tmp_basis)
610 62 : NULLIFY (qs_loc_env, loc_section, mos, particle_set, rho, rho_ao, mo_evals, cell)
611 62 : NULLIFY (mo_coeff, matrix_ks, admm_env, dummy_section)
612 :
613 : ! XAS TDP control type initialization
614 62 : CALL get_qs_env(qs_env, dft_control=dft_control, do_rixs=do_rixs)
615 :
616 62 : IF (do_rixs) THEN
617 14 : xas_tdp_section => section_vals_get_subs_vals(qs_env%input, "PROPERTIES%RIXS%XAS_TDP")
618 : ELSE
619 48 : xas_tdp_section => section_vals_get_subs_vals(qs_env%input, "DFT%XAS_TDP")
620 : END IF
621 :
622 62 : CALL xas_tdp_control_create(xas_tdp_control)
623 62 : CALL read_xas_tdp_control(xas_tdp_control, xas_tdp_section)
624 :
625 : ! Check the qs_env for a LSD/ROKS calculation
626 62 : IF (dft_control%uks) xas_tdp_control%do_uks = .TRUE.
627 62 : IF (dft_control%roks) xas_tdp_control%do_roks = .TRUE.
628 62 : do_uks = xas_tdp_control%do_uks
629 62 : do_os = do_uks .OR. xas_tdp_control%do_roks
630 :
631 : ! XAS TDP environment type initialization
632 62 : IF (PRESENT(rixs_env)) THEN
633 14 : xas_tdp_env => rixs_env%core_state
634 : ELSE
635 48 : CALL xas_tdp_env_create(xas_tdp_env)
636 : END IF
637 :
638 : ! Retrieving the excited atoms indices and correspondig state types
639 62 : IF (xas_tdp_control%define_excited == xas_tdp_by_index) THEN
640 :
641 : ! simply copy indices from xas_tdp_control
642 34 : nex_atoms = SIZE(xas_tdp_control%list_ex_atoms)
643 34 : CALL set_xas_tdp_env(xas_tdp_env, nex_atoms=nex_atoms)
644 102 : ALLOCATE (xas_tdp_env%ex_atom_indices(nex_atoms))
645 136 : ALLOCATE (xas_tdp_env%state_types(SIZE(xas_tdp_control%state_types, 1), nex_atoms))
646 114 : xas_tdp_env%ex_atom_indices = xas_tdp_control%list_ex_atoms
647 194 : xas_tdp_env%state_types = xas_tdp_control%state_types
648 :
649 : ! Test that these indices are within the range of available atoms
650 34 : CALL get_qs_env(qs_env=qs_env, natom=natom)
651 74 : IF (ANY(xas_tdp_env%ex_atom_indices > natom)) THEN
652 0 : CPABORT("Invalid index for the ATOM_LIST keyword.")
653 : END IF
654 :
655 : ! Check atom kinds and fill corresponding array
656 68 : ALLOCATE (xas_tdp_env%ex_kind_indices(nex_atoms))
657 74 : xas_tdp_env%ex_kind_indices = 0
658 34 : k = 0
659 34 : CALL get_qs_env(qs_env, particle_set=particle_set)
660 74 : DO i = 1, nex_atoms
661 40 : at_ind = xas_tdp_env%ex_atom_indices(i)
662 40 : CALL get_atomic_kind(particle_set(at_ind)%atomic_kind, kind_number=j)
663 122 : IF (ALL(ABS(xas_tdp_env%ex_kind_indices - j) /= 0)) THEN
664 38 : k = k + 1
665 38 : xas_tdp_env%ex_kind_indices(k) = j
666 : END IF
667 : END DO
668 34 : nex_kinds = k
669 34 : CALL set_xas_tdp_env(xas_tdp_env, nex_kinds=nex_kinds)
670 34 : CALL reallocate(xas_tdp_env%ex_kind_indices, 1, nex_kinds)
671 :
672 28 : ELSE IF (xas_tdp_control%define_excited == xas_tdp_by_kind) THEN
673 :
674 : ! need to find out which atom of which kind is excited
675 28 : CALL get_qs_env(qs_env=qs_env, atomic_kind_set=at_kind_set)
676 28 : n_kinds = SIZE(at_kind_set)
677 28 : nex_atoms = 0
678 :
679 28 : nex_kinds = SIZE(xas_tdp_control%list_ex_kinds)
680 84 : ALLOCATE (xas_tdp_env%ex_kind_indices(nex_kinds))
681 28 : k = 0
682 :
683 84 : DO i = 1, n_kinds
684 : CALL get_atomic_kind(atomic_kind=at_kind_set(i), name=kind_name, &
685 56 : natom=nat_of_kind, kind_number=kind_ind)
686 114 : IF (ANY(xas_tdp_control%list_ex_kinds == kind_name)) THEN
687 30 : nex_atoms = nex_atoms + nat_of_kind
688 30 : k = k + 1
689 30 : xas_tdp_env%ex_kind_indices(k) = kind_ind
690 : END IF
691 : END DO
692 :
693 84 : ALLOCATE (xas_tdp_env%ex_atom_indices(nex_atoms))
694 112 : ALLOCATE (xas_tdp_env%state_types(SIZE(xas_tdp_control%state_types, 1), nex_atoms))
695 28 : nex_atoms = 0
696 28 : nmatch = 0
697 :
698 84 : DO i = 1, n_kinds
699 : CALL get_atomic_kind(atomic_kind=at_kind_set(i), name=kind_name, &
700 56 : natom=nat_of_kind, atom_list=ind_of_kind)
701 146 : DO j = 1, nex_kinds
702 118 : IF (xas_tdp_control%list_ex_kinds(j) == kind_name) THEN
703 98 : xas_tdp_env%ex_atom_indices(nex_atoms + 1:nex_atoms + nat_of_kind) = ind_of_kind
704 70 : DO k = 1, SIZE(xas_tdp_control%state_types, 1)
705 : xas_tdp_env%state_types(k, nex_atoms + 1:nex_atoms + nat_of_kind) = &
706 114 : xas_tdp_control%state_types(k, j)
707 : END DO
708 30 : nex_atoms = nex_atoms + nat_of_kind
709 30 : nmatch = nmatch + 1
710 : END IF
711 : END DO
712 : END DO
713 :
714 28 : CALL set_xas_tdp_env(xas_tdp_env, nex_atoms=nex_atoms, nex_kinds=nex_kinds)
715 :
716 : ! Verifying that the input was valid
717 28 : IF (nmatch /= SIZE(xas_tdp_control%list_ex_kinds)) THEN
718 0 : CPABORT("Invalid kind(s) for the KIND_LIST keyword.")
719 : END IF
720 :
721 : END IF
722 :
723 : ! Sort the excited atoms indices (for convinience and use of locate function)
724 62 : CALL sort_unique(xas_tdp_env%ex_atom_indices, unique)
725 62 : IF (.NOT. unique) THEN
726 0 : CPABORT("Excited atoms not uniquely defined.")
727 : END IF
728 :
729 : ! Check for periodicity
730 62 : CALL get_qs_env(qs_env, cell=cell)
731 200 : IF (ALL(cell%perd == 0)) THEN
732 46 : xas_tdp_control%is_periodic = .FALSE.
733 64 : ELSE IF (ALL(cell%perd == 1)) THEN
734 16 : xas_tdp_control%is_periodic = .TRUE.
735 : ELSE
736 0 : CPABORT("XAS TDP only implemented for full PBCs or non-PBCs")
737 : END IF
738 :
739 : ! Allocating memory for the array of donor states
740 220 : n_donor_states = COUNT(xas_tdp_env%state_types /= xas_not_excited)
741 270 : ALLOCATE (xas_tdp_env%donor_states(n_donor_states))
742 146 : DO i = 1, n_donor_states
743 146 : CALL donor_state_create(xas_tdp_env%donor_states(i))
744 : END DO
745 :
746 : ! In case of ADMM, for the whole duration of the XAS_TDP, we need the total KS matrix
747 62 : IF (dft_control%do_admm) THEN
748 6 : CALL get_qs_env(qs_env, admm_env=admm_env, matrix_ks=matrix_ks)
749 :
750 12 : DO ispin = 1, dft_control%nspins
751 12 : CALL admm_correct_for_eigenvalues(ispin, admm_env, matrix_ks(ispin)%matrix)
752 : END DO
753 : END IF
754 :
755 : ! In case of externally imposed EPS_PGF_XAS, need to update ORB and RI_XAS interaction radii
756 62 : IF (xas_tdp_control%eps_pgf > 0.0_dp) THEN
757 0 : CALL get_qs_env(qs_env, qs_kind_set=qs_kind_set)
758 :
759 0 : DO i = 1, SIZE(qs_kind_set)
760 0 : CALL get_qs_kind(qs_kind_set(i), basis_set=tmp_basis, basis_type="ORB")
761 0 : CALL init_interaction_radii_orb_basis(tmp_basis, eps_pgf_orb=xas_tdp_control%eps_pgf)
762 0 : CALL get_qs_kind(qs_kind_set(i), basis_set=tmp_basis, basis_type="RI_XAS")
763 0 : CALL init_interaction_radii_orb_basis(tmp_basis, eps_pgf_orb=xas_tdp_control%eps_pgf)
764 : END DO
765 : END IF
766 :
767 : ! In case of ground state OT optimization, compute the MO eigenvalues and get canonical MOs
768 62 : IF (qs_env%scf_env%method == ot_method_nr) THEN
769 :
770 6 : CALL get_qs_env(qs_env, mos=mos, matrix_ks=matrix_ks)
771 6 : nspins = 1; IF (do_uks) nspins = 2
772 :
773 12 : DO ispin = 1, nspins
774 6 : CALL get_mo_set(mos(ispin), mo_coeff=mo_coeff, eigenvalues=mo_evals)
775 12 : CALL calculate_subspace_eigenvalues(mo_coeff, matrix_ks(ispin)%matrix, evals_arg=mo_evals)
776 : END DO
777 : END IF
778 :
779 : ! Initializing the qs_loc_env from the LOCALIZE subsection of XAS_TDP (largely inpired by MI's XAS)
780 : ! We create the LOCALIZE subsection here, since it is completely overwritten anyways
781 62 : CALL create_localize_section(dummy_section)
782 62 : CALL section_vals_create(xas_tdp_control%loc_subsection, dummy_section)
783 : CALL section_vals_val_set(xas_tdp_control%loc_subsection, "_SECTION_PARAMETERS_", &
784 62 : l_val=xas_tdp_control%do_loc)
785 62 : CALL section_release(dummy_section)
786 : xas_tdp_control%print_loc_subsection => section_vals_get_subs_vals( &
787 62 : xas_tdp_control%loc_subsection, "PRINT")
788 :
789 434 : ALLOCATE (xas_tdp_env%qs_loc_env)
790 62 : CALL qs_loc_env_create(xas_tdp_env%qs_loc_env)
791 62 : qs_loc_env => xas_tdp_env%qs_loc_env
792 62 : loc_section => xas_tdp_control%loc_subsection
793 : ! getting the number of MOs
794 62 : CALL get_qs_env(qs_env, mos=mos)
795 62 : CALL get_mo_set(mos(1), nmo=n_mo(1), homo=homo(1), nao=nao)
796 62 : n_mo(2) = n_mo(1)
797 62 : homo(2) = homo(1)
798 62 : nspins = 1
799 62 : IF (do_os) CALL get_mo_set(mos(2), nmo=n_mo(2), homo=homo(2))
800 62 : IF (do_uks) nspins = 2 !in roks, same MOs for both spins
801 :
802 : ! by default, all (doubly occupied) homo are localized
803 186 : IF (xas_tdp_control%n_search < 0 .OR. xas_tdp_control%n_search > MINVAL(homo)) &
804 0 : xas_tdp_control%n_search = MINVAL(homo)
805 : CALL qs_loc_control_init(qs_loc_env, loc_section, do_homo=.TRUE., do_xas=.TRUE., &
806 62 : nloc_xas=xas_tdp_control%n_search, spin_xas=1)
807 :
808 : ! do_xas argument above only prepares spin-alpha localization
809 62 : IF (do_uks) THEN
810 8 : qs_loc_env%localized_wfn_control%nloc_states(2) = xas_tdp_control%n_search
811 8 : qs_loc_env%localized_wfn_control%lu_bound_states(1, 2) = 1
812 8 : qs_loc_env%localized_wfn_control%lu_bound_states(2, 2) = xas_tdp_control%n_search
813 : END IF
814 :
815 : ! final qs_loc_env initialization. Impose Berry operator
816 62 : qs_loc_env%localized_wfn_control%operator_type = op_loc_berry
817 62 : qs_loc_env%localized_wfn_control%max_iter = 25000
818 62 : IF (.NOT. xas_tdp_control%do_loc) THEN
819 28 : qs_loc_env%localized_wfn_control%localization_method = do_loc_none
820 : ELSE
821 102 : n_moloc = qs_loc_env%localized_wfn_control%nloc_states
822 34 : CALL set_loc_centers(qs_loc_env%localized_wfn_control, n_moloc, nspins)
823 34 : IF (do_uks) THEN
824 : CALL qs_loc_env_init(qs_loc_env, qs_loc_env%localized_wfn_control, &
825 2 : qs_env, do_localize=.TRUE.)
826 : ELSE
827 : CALL qs_loc_env_init(qs_loc_env, qs_loc_env%localized_wfn_control, &
828 32 : qs_env, do_localize=.TRUE., myspin=1)
829 : END IF
830 : END IF
831 :
832 : ! Allocating memory for the array of excited atoms MOs. Worst case senario, all searched MOs are
833 : ! associated to the same atom
834 310 : ALLOCATE (xas_tdp_env%mos_of_ex_atoms(xas_tdp_control%n_search, nex_atoms, nspins))
835 :
836 : ! Compute the projector on the unoccupied, unperturbed ground state: Q = 1 - SP, sor each spin
837 62 : IF (do_os) nspins = 2
838 62 : CALL get_qs_env(qs_env, rho=rho, matrix_s=matrix_s)
839 62 : CALL qs_rho_get(rho, rho_ao=rho_ao)
840 :
841 258 : ALLOCATE (xas_tdp_env%q_projector(nspins))
842 62 : ALLOCATE (xas_tdp_env%q_projector(1)%matrix)
843 : CALL dbcsr_create(xas_tdp_env%q_projector(1)%matrix, name="Q PROJECTOR ALPHA", &
844 62 : template=matrix_s(1)%matrix, matrix_type=dbcsr_type_no_symmetry)
845 62 : IF (do_os) THEN
846 10 : ALLOCATE (xas_tdp_env%q_projector(2)%matrix)
847 : CALL dbcsr_create(xas_tdp_env%q_projector(2)%matrix, name="Q PROJECTOR BETA", &
848 10 : template=matrix_s(1)%matrix, matrix_type=dbcsr_type_no_symmetry)
849 : END IF
850 :
851 : ! In the case of spin-restricted calculations, rho_ao includes double occupency => 0.5 prefactor
852 62 : fact = -0.5_dp; IF (do_os) fact = -1.0_dp
853 : CALL dbcsr_multiply('N', 'N', fact, matrix_s(1)%matrix, rho_ao(1)%matrix, 0.0_dp, &
854 62 : xas_tdp_env%q_projector(1)%matrix, filter_eps=xas_tdp_control%eps_filter)
855 62 : CALL dbcsr_add_on_diag(xas_tdp_env%q_projector(1)%matrix, 1.0_dp)
856 62 : CALL dbcsr_finalize(xas_tdp_env%q_projector(1)%matrix)
857 :
858 62 : IF (do_os) THEN
859 : CALL dbcsr_multiply('N', 'N', fact, matrix_s(1)%matrix, rho_ao(2)%matrix, 0.0_dp, &
860 10 : xas_tdp_env%q_projector(2)%matrix, filter_eps=xas_tdp_control%eps_filter)
861 10 : CALL dbcsr_add_on_diag(xas_tdp_env%q_projector(2)%matrix, 1.0_dp)
862 10 : CALL dbcsr_finalize(xas_tdp_env%q_projector(2)%matrix)
863 : END IF
864 :
865 : ! Create the structure for the dipole in the AO basis
866 248 : ALLOCATE (xas_tdp_env%dipmat(3))
867 248 : DO i = 1, 3
868 186 : ALLOCATE (xas_tdp_env%dipmat(i)%matrix)
869 186 : CALL dbcsr_copy(matrix_tmp, matrix_s(1)%matrix, name="XAS TDP dipole matrix")
870 186 : IF (xas_tdp_control%dipole_form == xas_dip_vel) THEN
871 : CALL dbcsr_create(xas_tdp_env%dipmat(i)%matrix, template=matrix_s(1)%matrix, &
872 120 : matrix_type=dbcsr_type_antisymmetric)
873 120 : CALL dbcsr_complete_redistribute(matrix_tmp, xas_tdp_env%dipmat(i)%matrix)
874 : ELSE
875 : CALL dbcsr_create(xas_tdp_env%dipmat(i)%matrix, template=matrix_s(1)%matrix, &
876 66 : matrix_type=dbcsr_type_symmetric)
877 66 : CALL dbcsr_copy(xas_tdp_env%dipmat(i)%matrix, matrix_tmp)
878 : END IF
879 186 : CALL dbcsr_set(xas_tdp_env%dipmat(i)%matrix, 0.0_dp)
880 248 : CALL dbcsr_release(matrix_tmp)
881 : END DO
882 :
883 : ! Create the structure for the electric quadrupole in the AO basis, if required
884 62 : IF (xas_tdp_control%do_quad) THEN
885 0 : ALLOCATE (xas_tdp_env%quadmat(6))
886 0 : DO i = 1, 6
887 0 : ALLOCATE (xas_tdp_env%quadmat(i)%matrix)
888 0 : CALL dbcsr_copy(xas_tdp_env%quadmat(i)%matrix, matrix_s(1)%matrix, name="XAS TDP quadrupole matrix")
889 0 : CALL dbcsr_set(xas_tdp_env%quadmat(i)%matrix, 0.0_dp)
890 : END DO
891 : END IF
892 :
893 : ! Precompute it in the velocity representation, if so chosen
894 62 : IF (xas_tdp_control%dipole_form == xas_dip_vel) THEN
895 : !enforce minimum image to avoid any PBCs related issues. Ok because very localized densities
896 40 : CALL p_xyz_ao(xas_tdp_env%dipmat, qs_env, minimum_image=.TRUE.)
897 : END IF
898 :
899 : ! Allocate SOC in AO basis matrices
900 62 : IF (xas_tdp_control%do_soc .OR. xas_tdp_control%do_gw2x) THEN
901 88 : ALLOCATE (xas_tdp_env%orb_soc(3))
902 88 : DO i = 1, 3
903 128 : ALLOCATE (xas_tdp_env%orb_soc(i)%matrix)
904 : END DO
905 : END IF
906 :
907 : ! Check that everything is allowed
908 62 : CALL safety_check(xas_tdp_control, qs_env)
909 :
910 : ! Initialize libint for the 3-center integrals
911 62 : CALL cp_libint_static_init()
912 :
913 : ! Compute LUMOs as guess for OT solver and/or for GW2X correction
914 62 : IF (xas_tdp_control%do_ot .OR. xas_tdp_control%do_gw2x) THEN
915 20 : CALL make_lumo_guess(xas_tdp_env, xas_tdp_control, qs_env)
916 : END IF
917 :
918 186 : END SUBROUTINE xas_tdp_init
919 :
920 : ! **************************************************************************************************
921 : !> \brief splits the excited atoms of a kind into batches for RI 3c integrals load balance
922 : !> \param ex_atoms_of_kind the excited atoms for the current kind, randomly shuffled
923 : !> \param nbatch number of batches to loop over
924 : !> \param batch_size standard size of a batch
925 : !> \param atoms_of_kind number of atoms for the current kind (excited or not)
926 : !> \param xas_tdp_env ...
927 : ! **************************************************************************************************
928 68 : SUBROUTINE get_ri_3c_batches(ex_atoms_of_kind, nbatch, batch_size, atoms_of_kind, xas_tdp_env)
929 :
930 : INTEGER, ALLOCATABLE, DIMENSION(:), INTENT(INOUT) :: ex_atoms_of_kind
931 : INTEGER, INTENT(OUT) :: nbatch
932 : INTEGER, INTENT(IN) :: batch_size
933 : INTEGER, DIMENSION(:), INTENT(IN) :: atoms_of_kind
934 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
935 :
936 : INTEGER :: iat, iatom, nex_atom
937 68 : TYPE(rng_stream_type), ALLOCATABLE :: rng_stream
938 :
939 : !Get the atoms from atoms_of_kind that are excited
940 68 : nex_atom = 0
941 300 : DO iat = 1, SIZE(atoms_of_kind)
942 232 : iatom = atoms_of_kind(iat)
943 462 : IF (.NOT. ANY(xas_tdp_env%ex_atom_indices == iatom)) CYCLE
944 300 : nex_atom = nex_atom + 1
945 : END DO
946 :
947 204 : ALLOCATE (ex_atoms_of_kind(nex_atom))
948 68 : nex_atom = 0
949 300 : DO iat = 1, SIZE(atoms_of_kind)
950 232 : iatom = atoms_of_kind(iat)
951 462 : IF (.NOT. ANY(xas_tdp_env%ex_atom_indices == iatom)) CYCLE
952 74 : nex_atom = nex_atom + 1
953 300 : ex_atoms_of_kind(nex_atom) = iatom
954 : END DO
955 :
956 : !We shuffle those atoms to spread them
957 68 : rng_stream = rng_stream_type(name="uniform_rng", distribution_type=UNIFORM)
958 68 : CALL rng_stream%shuffle(ex_atoms_of_kind(1:nex_atom))
959 :
960 68 : nbatch = nex_atom/batch_size
961 68 : IF (nbatch*batch_size /= nex_atom) nbatch = nbatch + 1
962 :
963 68 : END SUBROUTINE get_ri_3c_batches
964 :
965 : ! **************************************************************************************************
966 : !> \brief Checks for forbidden keywords combinations
967 : !> \param xas_tdp_control ...
968 : !> \param qs_env ...
969 : ! **************************************************************************************************
970 62 : SUBROUTINE safety_check(xas_tdp_control, qs_env)
971 :
972 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
973 : TYPE(qs_environment_type), POINTER :: qs_env
974 :
975 : TYPE(dft_control_type), POINTER :: dft_control
976 :
977 : !PB only available without exact exchange
978 : IF (xas_tdp_control%is_periodic .AND. xas_tdp_control%do_hfx &
979 62 : .AND. xas_tdp_control%x_potential%potential_type == do_potential_coulomb) THEN
980 0 : CPABORT("XAS TDP with Coulomb operator for exact exchange only supports non-periodic BCs")
981 : END IF
982 :
983 : !open-shell/closed-shell tests
984 62 : IF (xas_tdp_control%do_roks .OR. xas_tdp_control%do_uks) THEN
985 :
986 10 : IF (.NOT. (xas_tdp_control%do_spin_cons .OR. xas_tdp_control%do_spin_flip)) THEN
987 0 : CPABORT("Need spin-conserving and/or spin-flip excitations for open-shell systems")
988 : END IF
989 :
990 10 : IF (xas_tdp_control%do_singlet .OR. xas_tdp_control%do_triplet) THEN
991 0 : CPABORT("Singlet/triplet excitations only for restricted closed-shell systems")
992 : END IF
993 :
994 10 : IF (xas_tdp_control%do_soc .AND. .NOT. &
995 : (xas_tdp_control%do_spin_flip .AND. xas_tdp_control%do_spin_cons)) THEN
996 :
997 0 : CPABORT("Both spin-conserving and spin-flip excitations are required for SOC")
998 : END IF
999 : ELSE
1000 :
1001 52 : IF (.NOT. (xas_tdp_control%do_singlet .OR. xas_tdp_control%do_triplet)) THEN
1002 0 : CPABORT("Need singlet and/or triplet excitations for closed-shell systems")
1003 : END IF
1004 :
1005 52 : IF (xas_tdp_control%do_spin_cons .OR. xas_tdp_control%do_spin_flip) THEN
1006 0 : CPABORT("Spin-conserving/spin-flip excitations only for open-shell systems")
1007 : END IF
1008 :
1009 52 : IF (xas_tdp_control%do_soc .AND. .NOT. &
1010 : (xas_tdp_control%do_singlet .AND. xas_tdp_control%do_triplet)) THEN
1011 :
1012 0 : CPABORT("Both singlet and triplet excitations are needed for SOC")
1013 : END IF
1014 : END IF
1015 :
1016 : !Warn against using E_RANGE with SOC
1017 62 : IF (xas_tdp_control%do_soc .AND. xas_tdp_control%e_range > 0.0_dp) THEN
1018 0 : CPWARN("Using E_RANGE and SOC together may lead to crashes, use N_EXCITED for safety.")
1019 : END IF
1020 :
1021 : !TDA, full-TDDFT and diagonalization
1022 62 : IF (.NOT. xas_tdp_control%tamm_dancoff) THEN
1023 :
1024 6 : IF (xas_tdp_control%do_spin_flip) THEN
1025 0 : CPABORT("Spin-flip kernel only implemented for Tamm-Dancoff approximation")
1026 : END IF
1027 :
1028 6 : IF (xas_tdp_control%do_ot) THEN
1029 0 : CPABORT("OT diagonalization only available within the Tamm-Dancoff approximation")
1030 : END IF
1031 : END IF
1032 :
1033 : !GW2X, need hfx kernel and LOCALIZE
1034 62 : IF (xas_tdp_control%do_gw2x) THEN
1035 18 : IF (.NOT. xas_tdp_control%do_hfx) THEN
1036 0 : CPABORT("GW2x requires the definition of the EXACT_EXCHANGE kernel")
1037 : END IF
1038 18 : IF (.NOT. xas_tdp_control%do_loc) THEN
1039 0 : CPABORT("GW2X requires the LOCALIZE keyword in DONOR_STATES")
1040 : END IF
1041 : END IF
1042 :
1043 : !Only allow ADMM schemes that correct for eigenvalues
1044 62 : CALL get_qs_env(qs_env, dft_control=dft_control)
1045 62 : IF (dft_control%do_admm) THEN
1046 : IF ((.NOT. qs_env%admm_env%purification_method == do_admm_purify_none) .AND. &
1047 6 : (.NOT. qs_env%admm_env%purification_method == do_admm_purify_cauchy_subspace) .AND. &
1048 : (.NOT. qs_env%admm_env%purification_method == do_admm_purify_mo_diag)) THEN
1049 :
1050 0 : CPABORT("XAS_TDP only compatible with ADMM purification NONE, CAUCHY_SUBSPACE and MO_DIAG")
1051 :
1052 : END IF
1053 : END IF
1054 :
1055 62 : END SUBROUTINE safety_check
1056 :
1057 : ! **************************************************************************************************
1058 : !> \brief Prints some basic info about the chosen parameters
1059 : !> \param ou the output unis
1060 : !> \param xas_tdp_control ...
1061 : !> \param qs_env ...
1062 : ! **************************************************************************************************
1063 62 : SUBROUTINE print_info(ou, xas_tdp_control, qs_env)
1064 :
1065 : INTEGER, INTENT(IN) :: ou
1066 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1067 : TYPE(qs_environment_type), POINTER :: qs_env
1068 :
1069 : INTEGER :: i
1070 : REAL(dp) :: occ
1071 62 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_s
1072 : TYPE(dft_control_type), POINTER :: dft_control
1073 : TYPE(section_vals_type), POINTER :: input, kernel_section
1074 :
1075 62 : NULLIFY (input, kernel_section, dft_control, matrix_s)
1076 :
1077 62 : CALL get_qs_env(qs_env, input=input, dft_control=dft_control, matrix_s=matrix_s)
1078 :
1079 : !Overlap matrix sparsity
1080 62 : occ = dbcsr_get_occupation(matrix_s(1)%matrix)
1081 :
1082 62 : IF (ou <= 0) RETURN
1083 :
1084 : !Reference calculation
1085 31 : IF (xas_tdp_control%do_uks) THEN
1086 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1087 4 : "XAS_TDP| Reference calculation: Unrestricted Kohn-Sham"
1088 27 : ELSE IF (xas_tdp_control%do_roks) THEN
1089 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1090 1 : "XAS_TDP| Reference calculation: Restricted Open-Shell Kohn-Sham"
1091 : ELSE
1092 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1093 26 : "XAS_TDP| Reference calculation: Restricted Closed-Shell Kohn-Sham"
1094 : END IF
1095 :
1096 : !TDA
1097 31 : IF (xas_tdp_control%tamm_dancoff) THEN
1098 : WRITE (UNIT=ou, FMT="(T3,A)") &
1099 28 : "XAS_TDP| Tamm-Dancoff Approximation (TDA): On"
1100 : ELSE
1101 : WRITE (UNIT=ou, FMT="(T3,A)") &
1102 3 : "XAS_TDP| Tamm-Dancoff Approximation (TDA): Off"
1103 : END IF
1104 :
1105 : !Dipole form
1106 31 : IF (xas_tdp_control%dipole_form == xas_dip_vel) THEN
1107 : WRITE (UNIT=ou, FMT="(T3,A)") &
1108 20 : "XAS_TDP| Transition Dipole Representation: VELOCITY"
1109 : ELSE
1110 : WRITE (UNIT=ou, FMT="(T3,A)") &
1111 11 : "XAS_TDP| Transition Dipole Representation: LENGTH"
1112 : END IF
1113 :
1114 : !Quadrupole
1115 31 : IF (xas_tdp_control%do_quad) THEN
1116 : WRITE (UNIT=ou, FMT="(T3,A)") &
1117 0 : "XAS_TDP| Transition Quadrupole: On"
1118 : END IF
1119 :
1120 : !EPS_PGF
1121 31 : IF (xas_tdp_control%eps_pgf > 0.0_dp) THEN
1122 : WRITE (UNIT=ou, FMT="(T3,A,ES7.1)") &
1123 0 : "XAS_TDP| EPS_PGF_XAS: ", xas_tdp_control%eps_pgf
1124 : ELSE
1125 : WRITE (UNIT=ou, FMT="(T3,A,ES7.1,A)") &
1126 31 : "XAS_TDP| EPS_PGF_XAS: ", dft_control%qs_control%eps_pgf_orb, " (= EPS_PGF_ORB)"
1127 : END IF
1128 :
1129 : !EPS_FILTER
1130 : WRITE (UNIT=ou, FMT="(T3,A,ES7.1)") &
1131 31 : "XAS_TDP| EPS_FILTER: ", xas_tdp_control%eps_filter
1132 :
1133 : !Grid info
1134 31 : IF (xas_tdp_control%do_xc) THEN
1135 : WRITE (UNIT=ou, FMT="(T3,A)") &
1136 26 : "XAS_TDP| Radial Grid(s) Info: Kind, na, nr"
1137 55 : DO i = 1, SIZE(xas_tdp_control%grid_info, 1)
1138 : WRITE (UNIT=ou, FMT="(T3,A,A6,A,A,A,A)") &
1139 29 : " ", TRIM(xas_tdp_control%grid_info(i, 1)), ", ", &
1140 84 : TRIM(xas_tdp_control%grid_info(i, 2)), ", ", TRIM(xas_tdp_control%grid_info(i, 3))
1141 : END DO
1142 : END IF
1143 :
1144 : !No kernel
1145 31 : IF (.NOT. xas_tdp_control%do_coulomb) THEN
1146 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1147 0 : "XAS_TDP| No kernel (standard DFT)"
1148 : END IF
1149 :
1150 : !XC kernel
1151 31 : IF (xas_tdp_control%do_xc) THEN
1152 :
1153 : WRITE (UNIT=ou, FMT="(/,T3,A,F5.2,A)") &
1154 26 : "XAS_TDP| RI Region's Radius: ", xas_tdp_control%ri_radius*angstrom, " Ang"
1155 :
1156 : WRITE (UNIT=ou, FMT="(T3,A,/)") &
1157 26 : "XAS_TDP| XC Kernel Functional(s) used for the kernel:"
1158 :
1159 26 : IF (qs_env%do_rixs) THEN
1160 7 : kernel_section => section_vals_get_subs_vals(input, "PROPERTIES%RIXS%XAS_TDP%KERNEL")
1161 : ELSE
1162 19 : kernel_section => section_vals_get_subs_vals(input, "DFT%XAS_TDP%KERNEL")
1163 : END IF
1164 26 : CALL xc_write(ou, kernel_section, lsd=.TRUE.)
1165 : END IF
1166 :
1167 : !HFX kernel
1168 31 : IF (xas_tdp_control%do_hfx) THEN
1169 : WRITE (UNIT=ou, FMT="(/,T3,A,/,/,T3,A,F5.3)") &
1170 22 : "XAS_TDP| Exact Exchange Kernel: Yes ", &
1171 44 : "EXACT_EXCHANGE| Scale: ", xas_tdp_control%sx
1172 22 : IF (xas_tdp_control%x_potential%potential_type == do_potential_coulomb) THEN
1173 : WRITE (UNIT=ou, FMT="(T3,A)") &
1174 15 : "EXACT_EXCHANGE| Potential : Coulomb"
1175 7 : ELSE IF (xas_tdp_control%x_potential%potential_type == do_potential_truncated) THEN
1176 : WRITE (UNIT=ou, FMT="(T3,A,/,T3,A,F5.2,A,/,T3,A,A)") &
1177 3 : "EXACT_EXCHANGE| Potential: Truncated Coulomb", &
1178 3 : "EXACT_EXCHANGE| Range: ", xas_tdp_control%x_potential%cutoff_radius*angstrom, ", (Ang)", &
1179 6 : "EXACT_EXCHANGE| T_C_G_DATA: ", TRIM(xas_tdp_control%x_potential%filename)
1180 4 : ELSE IF (xas_tdp_control%x_potential%potential_type == do_potential_short) THEN
1181 : WRITE (UNIT=ou, FMT="(T3,A,/,T3,A,F5.2,A,/,T3,A,F5.2,A,/,T3,A,ES7.1)") &
1182 4 : "EXACT_EXCHANGE| Potential: Short Range", &
1183 4 : "EXACT_EXCHANGE| Omega: ", xas_tdp_control%x_potential%omega, ", (1/a0)", &
1184 4 : "EXACT_EXCHANGE| Effective Range: ", xas_tdp_control%x_potential%cutoff_radius*angstrom, ", (Ang)", &
1185 8 : "EXACT_EXCHANGE| EPS_RANGE: ", xas_tdp_control%eps_range
1186 : END IF
1187 22 : IF (xas_tdp_control%eps_screen > 1.0E-16) THEN
1188 : WRITE (UNIT=ou, FMT="(T3,A,ES7.1)") &
1189 22 : "EXACT_EXCHANGE| EPS_SCREENING: ", xas_tdp_control%eps_screen
1190 : END IF
1191 :
1192 : !RI metric
1193 22 : IF (xas_tdp_control%do_ri_metric) THEN
1194 :
1195 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1196 3 : "EXACT_EXCHANGE| Using a RI metric"
1197 3 : IF (xas_tdp_control%ri_m_potential%potential_type == do_potential_id) THEN
1198 : WRITE (UNIT=ou, FMT="(T3,A)") &
1199 1 : "EXACT_EXCHANGE RI_METRIC| Potential : Overlap"
1200 2 : ELSE IF (xas_tdp_control%ri_m_potential%potential_type == do_potential_truncated) THEN
1201 : WRITE (UNIT=ou, FMT="(T3,A,/,T3,A,F5.2,A,/,T3,A,A)") &
1202 1 : "EXACT_EXCHANGE RI_METRIC| Potential: Truncated Coulomb", &
1203 1 : "EXACT_EXCHANGE RI_METRIC| Range: ", xas_tdp_control%ri_m_potential%cutoff_radius &
1204 1 : *angstrom, ", (Ang)", &
1205 2 : "EXACT_EXCHANGE RI_METRIC| T_C_G_DATA: ", TRIM(xas_tdp_control%ri_m_potential%filename)
1206 1 : ELSE IF (xas_tdp_control%ri_m_potential%potential_type == do_potential_short) THEN
1207 : WRITE (UNIT=ou, FMT="(T3,A,/,T3,A,F5.2,A,/,T3,A,F5.2,A,/,T3,A,ES7.1)") &
1208 1 : "EXACT_EXCHANGE RI_METRIC| Potential: Short Range", &
1209 1 : "EXACT_EXCHANGE RI_METRIC| Omega: ", xas_tdp_control%ri_m_potential%omega, ", (1/a0)", &
1210 1 : "EXACT_EXCHANGE RI_METRIC| Effective Range: ", &
1211 1 : xas_tdp_control%ri_m_potential%cutoff_radius*angstrom, ", (Ang)", &
1212 2 : "EXACT_EXCHANGE RI_METRIC| EPS_RANGE: ", xas_tdp_control%eps_range
1213 : END IF
1214 : END IF
1215 : ELSE
1216 : WRITE (UNIT=ou, FMT="(/,T3,A,/)") &
1217 9 : "XAS_TDP| Exact Exchange Kernel: No "
1218 : END IF
1219 :
1220 : !overlap mtrix occupation
1221 : WRITE (UNIT=ou, FMT="(/,T3,A,F5.2)") &
1222 31 : "XAS_TDP| Overlap matrix occupation: ", occ
1223 :
1224 : !GW2X parameter
1225 31 : IF (xas_tdp_control%do_gw2x) THEN
1226 : WRITE (UNIT=ou, FMT="(T3,A,/)") &
1227 9 : "XAS_TDP| GW2X correction enabled"
1228 :
1229 9 : IF (xas_tdp_control%xps_only) THEN
1230 : WRITE (UNIT=ou, FMT="(T3,A)") &
1231 2 : "GW2X| Only computing ionizations potentials for XPS"
1232 : END IF
1233 :
1234 9 : IF (xas_tdp_control%pseudo_canonical) THEN
1235 : WRITE (UNIT=ou, FMT="(T3,A)") &
1236 8 : "GW2X| Using the pseudo-canonical scheme"
1237 : ELSE
1238 : WRITE (UNIT=ou, FMT="(T3,A)") &
1239 1 : "GW2X| Using the GW2X* scheme"
1240 : END IF
1241 :
1242 : WRITE (UNIT=ou, FMT="(T3,A,ES7.1)") &
1243 9 : "GW2X| EPS_GW2X: ", xas_tdp_control%gw2x_eps
1244 :
1245 : WRITE (UNIT=ou, FMT="(T3,A,I5)") &
1246 9 : "GW2X| contraction batch size: ", xas_tdp_control%batch_size
1247 :
1248 9 : IF ((INT(xas_tdp_control%c_os) /= 1) .OR. (INT(xas_tdp_control%c_ss) /= 1)) THEN
1249 : WRITE (UNIT=ou, FMT="(T3,A,F7.4,/,T3,A,F7.4)") &
1250 1 : "GW2X| Same-spin scaling factor: ", xas_tdp_control%c_ss, &
1251 2 : "GW2X| Opposite-spin scaling factor: ", xas_tdp_control%c_os
1252 : END IF
1253 :
1254 : END IF
1255 :
1256 62 : END SUBROUTINE print_info
1257 :
1258 : ! **************************************************************************************************
1259 : !> \brief Assosciate (possibly localized) lowest energy MOs to each excited atoms. The procedure
1260 : !> looks for MOs "centered" on the excited atoms by comparing distances. It
1261 : !> then fills the mos_of_ex_atoms arrays of the xas_tdp_env. Only the xas_tdp_control%n_search
1262 : !> lowest energy MOs are considered. Largely inspired by MI's implementation of XAS
1263 : !> It is assumed that the Berry phase is used to compute centers.
1264 : !> \param xas_tdp_env ...
1265 : !> \param xas_tdp_control ...
1266 : !> \param qs_env ...
1267 : !> \note Whether localization took place or not, the procedure is the same as centers are stored in
1268 : !> xas_tdp_env%qs_loc_env%localized_wfn_control%centers_set
1269 : !> Assumes that find_mo_centers has been run previously
1270 : ! **************************************************************************************************
1271 62 : SUBROUTINE assign_mos_to_ex_atoms(xas_tdp_env, xas_tdp_control, qs_env)
1272 :
1273 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1274 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1275 : TYPE(qs_environment_type), POINTER :: qs_env
1276 :
1277 : INTEGER :: at_index, iat, iat_memo, imo, ispin, &
1278 : n_atoms, n_search, nex_atoms, nspins
1279 : INTEGER, DIMENSION(3) :: perd_init
1280 62 : INTEGER, DIMENSION(:, :, :), POINTER :: mos_of_ex_atoms
1281 : REAL(dp) :: dist, dist_min
1282 : REAL(dp), DIMENSION(3) :: at_pos, r_ac, wfn_center
1283 : TYPE(cell_type), POINTER :: cell
1284 : TYPE(localized_wfn_control_type), POINTER :: localized_wfn_control
1285 62 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
1286 :
1287 62 : NULLIFY (localized_wfn_control, mos_of_ex_atoms, cell, particle_set)
1288 :
1289 : ! Initialization. mos_of_ex_atoms filled with -1, meaning no assigned state
1290 62 : mos_of_ex_atoms => xas_tdp_env%mos_of_ex_atoms
1291 602 : mos_of_ex_atoms(:, :, :) = -1
1292 62 : n_search = xas_tdp_control%n_search
1293 62 : nex_atoms = xas_tdp_env%nex_atoms
1294 62 : localized_wfn_control => xas_tdp_env%qs_loc_env%localized_wfn_control
1295 62 : CALL get_qs_env(qs_env=qs_env, particle_set=particle_set, cell=cell)
1296 62 : n_atoms = SIZE(particle_set)
1297 62 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
1298 :
1299 : ! Temporarly impose periodic BCs because of Berry's phase operator used for localization
1300 248 : perd_init = cell%perd
1301 248 : cell%perd = 1
1302 :
1303 : ! Loop over n_search lowest energy MOs and all atoms, for each spin
1304 132 : DO ispin = 1, nspins
1305 430 : DO imo = 1, n_search
1306 : ! retrieve MO wave function center coordinates.
1307 1192 : wfn_center(1:3) = localized_wfn_control%centers_set(ispin)%array(1:3, imo)
1308 298 : iat_memo = 0
1309 :
1310 : ! a large enough value to avoid bad surprises
1311 298 : dist_min = 10000.0_dp
1312 7708 : DO iat = 1, n_atoms
1313 29640 : at_pos = particle_set(iat)%r
1314 7410 : r_ac = pbc(at_pos, wfn_center, cell)
1315 29640 : dist = NORM2(r_ac)
1316 :
1317 : ! keep memory of which atom is the closest to the wave function center
1318 7708 : IF (dist < dist_min) THEN
1319 674 : iat_memo = iat
1320 674 : dist_min = dist
1321 : END IF
1322 : END DO
1323 :
1324 : ! Verify that the closest atom is actually excited and assign the MO if so
1325 600 : IF (ANY(xas_tdp_env%ex_atom_indices == iat_memo)) THEN
1326 140 : at_index = locate(xas_tdp_env%ex_atom_indices, iat_memo)
1327 140 : mos_of_ex_atoms(imo, at_index, ispin) = 1
1328 : END IF
1329 : END DO !imo
1330 : END DO !ispin
1331 :
1332 : ! Go back to initial BCs
1333 248 : cell%perd = perd_init
1334 :
1335 62 : END SUBROUTINE assign_mos_to_ex_atoms
1336 :
1337 : ! **************************************************************************************************
1338 : !> \brief Re-initialize the qs_loc_env to the current MOs.
1339 : !> \param qs_loc_env the env to re-initialize
1340 : !> \param n_loc_states the number of states to include
1341 : !> \param do_uks in cas of spin unrestricted calculation, initialize for both spins
1342 : !> \param qs_env ...
1343 : !> \note Useful when one needs to make use of qs_loc features and it is either with canonical MOs
1344 : !> or the localized MOs have been modified. do_localize is overwritten.
1345 : !> Same loc range for both spins
1346 : ! **************************************************************************************************
1347 96 : SUBROUTINE reinit_qs_loc_env(qs_loc_env, n_loc_states, do_uks, qs_env)
1348 :
1349 : TYPE(qs_loc_env_type), POINTER :: qs_loc_env
1350 : INTEGER, INTENT(IN) :: n_loc_states
1351 : LOGICAL, INTENT(IN) :: do_uks
1352 : TYPE(qs_environment_type), POINTER :: qs_env
1353 :
1354 : INTEGER :: i, nspins
1355 : TYPE(localized_wfn_control_type), POINTER :: loc_wfn_control
1356 :
1357 : ! First, release the old env
1358 96 : CALL qs_loc_env_release(qs_loc_env)
1359 :
1360 : ! Re-create it
1361 96 : CALL qs_loc_env_create(qs_loc_env)
1362 96 : CALL localized_wfn_control_create(qs_loc_env%localized_wfn_control)
1363 96 : loc_wfn_control => qs_loc_env%localized_wfn_control
1364 :
1365 : ! Initialize it
1366 96 : loc_wfn_control%localization_method = do_loc_none
1367 96 : loc_wfn_control%operator_type = op_loc_berry
1368 288 : loc_wfn_control%nloc_states(:) = n_loc_states
1369 96 : loc_wfn_control%eps_occ = 0.0_dp
1370 288 : loc_wfn_control%lu_bound_states(1, :) = 1
1371 288 : loc_wfn_control%lu_bound_states(2, :) = n_loc_states
1372 96 : loc_wfn_control%set_of_states = state_loc_list
1373 96 : loc_wfn_control%do_homo = .TRUE.
1374 288 : ALLOCATE (loc_wfn_control%loc_states(n_loc_states, 2))
1375 592 : DO i = 1, n_loc_states
1376 1584 : loc_wfn_control%loc_states(i, :) = i
1377 : END DO
1378 :
1379 96 : nspins = 1; IF (do_uks) nspins = 2
1380 96 : CALL set_loc_centers(loc_wfn_control, loc_wfn_control%nloc_states, nspins=nspins)
1381 : ! need to set do_localize=.TRUE. because otherwise no routine works
1382 96 : IF (do_uks) THEN
1383 10 : CALL qs_loc_env_init(qs_loc_env, loc_wfn_control, qs_env, do_localize=.TRUE.)
1384 : ELSE
1385 86 : CALL qs_loc_env_init(qs_loc_env, loc_wfn_control, qs_env, myspin=1, do_localize=.TRUE.)
1386 : END IF
1387 :
1388 96 : END SUBROUTINE reinit_qs_loc_env
1389 :
1390 : ! *************************************************************************************************
1391 : !> \brief Diagonalize the subset of previously localized MOs that are associated to each excited
1392 : !> atoms. Updates the MO coeffs accordingly.
1393 : !> \param xas_tdp_env ...
1394 : !> \param xas_tdp_control ...
1395 : !> \param qs_env ...
1396 : !> \note Needed because after localization, the MOs loose their identity (1s, 2s , 2p, etc)
1397 : ! **************************************************************************************************
1398 34 : SUBROUTINE diagonalize_assigned_mo_subset(xas_tdp_env, xas_tdp_control, qs_env)
1399 :
1400 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1401 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1402 : TYPE(qs_environment_type), POINTER :: qs_env
1403 :
1404 : INTEGER :: i, iat, ilmo, ispin, nao, nlmo, nspins
1405 34 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: evals
1406 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
1407 : TYPE(cp_fm_struct_type), POINTER :: ks_struct, lmo_struct
1408 : TYPE(cp_fm_type) :: evecs, ks_fm, lmo_fm, work
1409 : TYPE(cp_fm_type), POINTER :: mo_coeff
1410 34 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks
1411 34 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
1412 : TYPE(mp_para_env_type), POINTER :: para_env
1413 :
1414 34 : NULLIFY (mos, mo_coeff, matrix_ks, para_env, blacs_env, lmo_struct, ks_struct)
1415 :
1416 : ! Get what we need from qs_env
1417 34 : CALL get_qs_env(qs_env, mos=mos, matrix_ks=matrix_ks, para_env=para_env, blacs_env=blacs_env)
1418 :
1419 34 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
1420 :
1421 : ! Loop over the excited atoms and spin
1422 70 : DO ispin = 1, nspins
1423 116 : DO iat = 1, xas_tdp_env%nex_atoms
1424 :
1425 : ! get the MOs
1426 46 : CALL get_mo_set(mos(ispin), mo_coeff=mo_coeff, nao=nao)
1427 :
1428 : ! count how many MOs are associated to this atom and create a fm/struct
1429 346 : nlmo = COUNT(xas_tdp_env%mos_of_ex_atoms(:, iat, ispin) == 1)
1430 : CALL cp_fm_struct_create(lmo_struct, nrow_global=nao, ncol_global=nlmo, &
1431 46 : para_env=para_env, context=blacs_env)
1432 46 : CALL cp_fm_create(lmo_fm, lmo_struct)
1433 46 : CALL cp_fm_create(work, lmo_struct)
1434 :
1435 : CALL cp_fm_struct_create(ks_struct, nrow_global=nlmo, ncol_global=nlmo, &
1436 46 : para_env=para_env, context=blacs_env)
1437 46 : CALL cp_fm_create(ks_fm, ks_struct)
1438 46 : CALL cp_fm_create(evecs, ks_struct)
1439 :
1440 : ! Loop over the localized MOs associated to this atom
1441 46 : i = 0
1442 346 : DO ilmo = 1, xas_tdp_control%n_search
1443 300 : IF (xas_tdp_env%mos_of_ex_atoms(ilmo, iat, ispin) == -1) CYCLE
1444 :
1445 62 : i = i + 1
1446 : ! put the coeff in our atom-restricted lmo_fm
1447 : CALL cp_fm_to_fm_submat(mo_coeff, lmo_fm, nrow=nao, ncol=1, s_firstrow=1, &
1448 346 : s_firstcol=ilmo, t_firstrow=1, t_firstcol=i)
1449 :
1450 : END DO !ilmo
1451 :
1452 : ! Computing the KS matrix in the subset of MOs
1453 46 : CALL cp_dbcsr_sm_fm_multiply(matrix_ks(ispin)%matrix, lmo_fm, work, ncol=nlmo)
1454 46 : CALL parallel_gemm('T', 'N', nlmo, nlmo, nao, 1.0_dp, lmo_fm, work, 0.0_dp, ks_fm)
1455 :
1456 : ! Diagonalizing the KS matrix in the subset of MOs
1457 138 : ALLOCATE (evals(nlmo))
1458 46 : CALL cp_fm_syevd(ks_fm, evecs, evals)
1459 46 : DEALLOCATE (evals)
1460 :
1461 : ! Express the MOs in the basis that diagonalizes KS
1462 46 : CALL parallel_gemm('N', 'N', nao, nlmo, nlmo, 1.0_dp, lmo_fm, evecs, 0.0_dp, work)
1463 :
1464 : ! Replacing the new MOs back in the MO coeffs
1465 46 : i = 0
1466 346 : DO ilmo = 1, xas_tdp_control%n_search
1467 300 : IF (xas_tdp_env%mos_of_ex_atoms(ilmo, iat, ispin) == -1) CYCLE
1468 :
1469 62 : i = i + 1
1470 : CALL cp_fm_to_fm_submat(work, mo_coeff, nrow=nao, ncol=1, s_firstrow=1, &
1471 346 : s_firstcol=i, t_firstrow=1, t_firstcol=ilmo)
1472 :
1473 : END DO
1474 :
1475 : ! Excited atom clean-up
1476 46 : CALL cp_fm_release(lmo_fm)
1477 46 : CALL cp_fm_release(work)
1478 46 : CALL cp_fm_struct_release(lmo_struct)
1479 46 : CALL cp_fm_release(ks_fm)
1480 46 : CALL cp_fm_release(evecs)
1481 220 : CALL cp_fm_struct_release(ks_struct)
1482 : END DO !iat
1483 : END DO !ispin
1484 :
1485 68 : END SUBROUTINE diagonalize_assigned_mo_subset
1486 :
1487 : ! **************************************************************************************************
1488 : !> \brief Assign core MO(s) to a given donor_state, taking the type (1S, 2S, etc) into account.
1489 : !> The projection on a representative Slater-type orbital basis is used as a indicator.
1490 : !> It is assumed that MOs are already assigned to excited atoms based on their center
1491 : !> \param donor_state the donor_state to which a MO must be assigned
1492 : !> \param xas_tdp_env ...
1493 : !> \param xas_tdp_control ...
1494 : !> \param qs_env ...
1495 : ! **************************************************************************************************
1496 84 : SUBROUTINE assign_mos_to_donor_state(donor_state, xas_tdp_env, xas_tdp_control, qs_env)
1497 :
1498 : TYPE(donor_state_type), POINTER :: donor_state
1499 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1500 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1501 : TYPE(qs_environment_type), POINTER :: qs_env
1502 :
1503 : INTEGER :: at_index, i, iat, imo, ispin, l, my_mo, &
1504 : n_search, n_states, nao, ndo_so, nj, &
1505 : nsgf_kind, nsgf_sto, nspins, &
1506 : output_unit, zval
1507 84 : INTEGER, ALLOCATABLE, DIMENSION(:, :) :: my_mos
1508 : INTEGER, DIMENSION(2) :: next_best_overlap_ind
1509 : INTEGER, DIMENSION(4, 7) :: ne
1510 84 : INTEGER, DIMENSION(:), POINTER :: first_sgf, lq, nq
1511 84 : INTEGER, DIMENSION(:, :, :), POINTER :: mos_of_ex_atoms
1512 : LOGICAL :: unique
1513 : REAL(dp) :: zeff
1514 84 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: diag, overlap, sto_overlap
1515 84 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: max_overlap
1516 : REAL(dp), DIMENSION(2) :: next_best_overlap
1517 84 : REAL(dp), DIMENSION(:), POINTER :: mo_evals, zeta
1518 84 : REAL(dp), DIMENSION(:, :), POINTER :: overlap_matrix, tmp_coeff
1519 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
1520 : TYPE(cp_fm_struct_type), POINTER :: eval_mat_struct, gs_struct, matrix_struct
1521 : TYPE(cp_fm_type) :: eval_mat, work_mat
1522 : TYPE(cp_fm_type), POINTER :: gs_coeffs, mo_coeff
1523 84 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks
1524 : TYPE(gto_basis_set_type), POINTER :: kind_basis_set, sto_to_gto_basis_set
1525 84 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
1526 : TYPE(mp_para_env_type), POINTER :: para_env
1527 84 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
1528 84 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
1529 : TYPE(sto_basis_set_type), POINTER :: sto_basis_set
1530 :
1531 84 : NULLIFY (sto_basis_set, sto_to_gto_basis_set, qs_kind_set, kind_basis_set, lq, nq, zeta)
1532 84 : NULLIFY (overlap_matrix, mos, mo_coeff, mos_of_ex_atoms, tmp_coeff, first_sgf, particle_set)
1533 84 : NULLIFY (mo_evals, matrix_ks, para_env, blacs_env)
1534 84 : NULLIFY (eval_mat_struct, gs_struct, gs_coeffs)
1535 :
1536 168 : output_unit = cp_logger_get_default_io_unit()
1537 :
1538 : CALL get_qs_env(qs_env=qs_env, qs_kind_set=qs_kind_set, mos=mos, particle_set=particle_set, &
1539 84 : matrix_ks=matrix_ks, para_env=para_env, blacs_env=blacs_env)
1540 :
1541 84 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
1542 :
1543 : ! Construction of a STO that fits the type of orbital we look for
1544 84 : ALLOCATE (zeta(1))
1545 84 : ALLOCATE (lq(1))
1546 84 : ALLOCATE (nq(1))
1547 : ! Retrieving quantum numbers
1548 84 : IF (donor_state%state_type == xas_1s_type) THEN
1549 70 : nq(1) = 1
1550 70 : lq(1) = 0
1551 70 : n_states = 1
1552 14 : ELSE IF (donor_state%state_type == xas_2s_type) THEN
1553 6 : nq(1) = 2
1554 6 : lq(1) = 0
1555 6 : n_states = 1
1556 8 : ELSE IF (donor_state%state_type == xas_2p_type) THEN
1557 8 : nq(1) = 2
1558 8 : lq(1) = 1
1559 8 : n_states = 3
1560 : ELSE
1561 0 : CPABORT("Procedure for required type not implemented")
1562 : END IF
1563 336 : ALLOCATE (my_mos(n_states, nspins))
1564 252 : ALLOCATE (max_overlap(n_states, nspins))
1565 :
1566 : ! Getting the atomic number
1567 84 : CALL get_qs_kind(qs_kind_set(donor_state%kind_index), zeff=zeff)
1568 84 : zval = INT(zeff)
1569 :
1570 : ! Electronic configuration (copied from MI's XAS)
1571 84 : ne = 0
1572 420 : DO l = 1, 4
1573 336 : nj = 2*(l - 1) + 1
1574 2268 : DO i = l, 7
1575 1848 : ne(l, i) = ptable(zval)%e_conv(l - 1) - 2*nj*(i - l)
1576 1848 : ne(l, i) = MAX(ne(l, i), 0)
1577 2184 : ne(l, i) = MIN(ne(l, i), 2*nj)
1578 : END DO
1579 : END DO
1580 :
1581 : ! computing zeta with the Slater sum rules
1582 84 : zeta(1) = srules(zval, ne, nq(1), lq(1))
1583 :
1584 : ! Allocating memory and initiate STO
1585 84 : CALL allocate_sto_basis_set(sto_basis_set)
1586 84 : CALL set_sto_basis_set(sto_basis_set, nshell=1, nq=nq, lq=lq, zet=zeta)
1587 :
1588 : ! Some clean-up
1589 84 : DEALLOCATE (nq, lq, zeta)
1590 :
1591 : ! Expanding the STO into (normalized) GTOs for later calculations, use standard 3 gaussians
1592 : CALL create_gto_from_sto_basis(sto_basis_set=sto_basis_set, &
1593 : gto_basis_set=sto_to_gto_basis_set, &
1594 84 : ngauss=3)
1595 84 : sto_to_gto_basis_set%norm_type = 2
1596 84 : CALL init_orb_basis_set(sto_to_gto_basis_set)
1597 :
1598 : ! Retrieving the atomic kind related GTO in which MOs are expanded
1599 84 : CALL get_qs_kind(qs_kind_set(donor_state%kind_index), basis_set=kind_basis_set)
1600 :
1601 : ! Allocating and computing the overlap between the two basis (they share the same center)
1602 84 : CALL get_gto_basis_set(gto_basis_set=kind_basis_set, nsgf=nsgf_kind)
1603 84 : CALL get_gto_basis_set(gto_basis_set=sto_to_gto_basis_set, nsgf=nsgf_sto)
1604 336 : ALLOCATE (overlap_matrix(nsgf_sto, nsgf_kind))
1605 :
1606 : ! Making use of MI's subroutine
1607 84 : CALL calc_stogto_overlap(sto_to_gto_basis_set, kind_basis_set, overlap_matrix)
1608 :
1609 : ! Some clean-up
1610 84 : CALL deallocate_sto_basis_set(sto_basis_set)
1611 84 : CALL deallocate_gto_basis_set(sto_to_gto_basis_set)
1612 :
1613 : ! Looping over the potential donor states to compute overlap with STO basis
1614 84 : mos_of_ex_atoms => xas_tdp_env%mos_of_ex_atoms
1615 84 : n_search = xas_tdp_control%n_search
1616 84 : at_index = donor_state%at_index
1617 84 : iat = locate(xas_tdp_env%ex_atom_indices, at_index)
1618 252 : ALLOCATE (first_sgf(SIZE(particle_set))) !probably do not need that
1619 84 : CALL get_particle_set(particle_set=particle_set, qs_kind_set=qs_kind_set, first_sgf=first_sgf)
1620 252 : ALLOCATE (tmp_coeff(nsgf_kind, 1))
1621 168 : ALLOCATE (sto_overlap(nsgf_kind))
1622 252 : ALLOCATE (overlap(n_search))
1623 :
1624 84 : next_best_overlap = 0.0_dp
1625 292 : max_overlap = 0.0_dp
1626 :
1627 178 : DO ispin = 1, nspins
1628 :
1629 94 : CALL get_mo_set(mos(ispin), mo_coeff=mo_coeff, nao=nao)
1630 530 : overlap = 0.0_dp
1631 :
1632 94 : my_mo = 0
1633 530 : DO imo = 1, n_search
1634 530 : IF (mos_of_ex_atoms(imo, iat, ispin) > 0) THEN
1635 :
1636 4410 : sto_overlap = 0.0_dp
1637 4600 : tmp_coeff = 0.0_dp
1638 :
1639 : ! Getting the relevant coefficients for the candidate state
1640 : CALL cp_fm_get_submatrix(fm=mo_coeff, target_m=tmp_coeff, start_row=first_sgf(at_index), &
1641 190 : start_col=imo, n_rows=nsgf_kind, n_cols=1, transpose=.FALSE.)
1642 :
1643 : ! Computing the product overlap_matrix*coeffs
1644 : CALL dgemm('N', 'N', nsgf_sto, 1, nsgf_kind, 1.0_dp, overlap_matrix, nsgf_sto, &
1645 190 : tmp_coeff, nsgf_kind, 0.0_dp, sto_overlap, nsgf_sto)
1646 :
1647 : ! Each element of column vector sto_overlap is the overlap of a basis element of the
1648 : ! generated STO basis with the kind specific orbital basis. Take the sum of the absolute
1649 : ! values so that rotation (of the px, py, pz for example) does not hinder our search
1650 4410 : overlap(imo) = SUM(ABS(sto_overlap))
1651 :
1652 : END IF
1653 : END DO
1654 :
1655 : ! Finding the best overlap(s)
1656 208 : DO i = 1, n_states
1657 650 : my_mo = MAXLOC(overlap, 1)
1658 114 : my_mos(i, ispin) = my_mo
1659 764 : max_overlap(i, ispin) = MAXVAL(overlap, 1)
1660 208 : overlap(my_mo) = 0.0_dp
1661 : END DO
1662 : ! Getting the next best overlap (for validation purposes)
1663 624 : next_best_overlap(ispin) = MAXVAL(overlap, 1)
1664 530 : next_best_overlap_ind(ispin) = MAXLOC(overlap, 1)
1665 :
1666 : ! Sort MO indices
1667 272 : CALL sort_unique(my_mos(:, ispin), unique)
1668 :
1669 : END DO !ispin
1670 :
1671 : ! Some clean-up
1672 84 : DEALLOCATE (overlap_matrix, tmp_coeff)
1673 :
1674 : ! Dealing with the result
1675 584 : IF (ALL(my_mos > 0) .AND. ALL(my_mos <= n_search)) THEN
1676 : ! Assigning the MO indices to the donor_state
1677 168 : ALLOCATE (donor_state%mo_indices(n_states, nspins))
1678 292 : donor_state%mo_indices = my_mos
1679 84 : donor_state%ndo_mo = n_states
1680 :
1681 : ! Storing the MOs in the donor_state, as vectors column: first columns alpha spin, then beta
1682 : CALL cp_fm_struct_create(gs_struct, nrow_global=nao, ncol_global=n_states*nspins, &
1683 84 : para_env=para_env, context=blacs_env)
1684 84 : ALLOCATE (donor_state%gs_coeffs)
1685 84 : CALL cp_fm_create(donor_state%gs_coeffs, gs_struct)
1686 :
1687 84 : IF (.NOT. ASSOCIATED(xas_tdp_env%mo_coeff)) THEN
1688 194 : ALLOCATE (xas_tdp_env%mo_coeff(nspins))
1689 : END IF
1690 :
1691 178 : DO ispin = 1, nspins
1692 94 : CALL get_mo_set(mos(ispin), mo_coeff=mo_coeff)
1693 : ! check if mo_coeff is copied before for another donor_state
1694 94 : IF (.NOT. ASSOCIATED(xas_tdp_env%mo_coeff(ispin)%local_data)) THEN
1695 : ! copy mo_coeff
1696 : CALL cp_fm_get_info(matrix=mo_coeff, &
1697 70 : matrix_struct=matrix_struct)
1698 70 : CALL cp_fm_create(xas_tdp_env%mo_coeff(ispin), matrix_struct)
1699 70 : CALL cp_fm_to_fm(mo_coeff, xas_tdp_env%mo_coeff(ispin))
1700 : END IF
1701 :
1702 292 : DO i = 1, n_states
1703 : CALL cp_fm_to_fm_submat(msource=mo_coeff, mtarget=donor_state%gs_coeffs, nrow=nao, &
1704 : ncol=1, s_firstrow=1, s_firstcol=my_mos(i, ispin), &
1705 208 : t_firstrow=1, t_firstcol=(ispin - 1)*n_states + i)
1706 : END DO
1707 : END DO
1708 84 : gs_coeffs => donor_state%gs_coeffs
1709 :
1710 : !Keep the subset of the coeffs centered on the excited atom as global array (used a lot)
1711 336 : ALLOCATE (donor_state%contract_coeffs(nsgf_kind, n_states*nspins))
1712 : CALL cp_fm_get_submatrix(gs_coeffs, donor_state%contract_coeffs, start_row=first_sgf(at_index), &
1713 84 : start_col=1, n_rows=nsgf_kind, n_cols=n_states*nspins)
1714 :
1715 : ! Assigning corresponding energy eigenvalues and writing some info in standard input file
1716 :
1717 : !standard eigenvalues as gotten from the KS diagonalization in the ground state
1718 84 : IF (.NOT. xas_tdp_control%do_loc .AND. .NOT. xas_tdp_control%do_roks) THEN
1719 32 : IF (output_unit > 0) THEN
1720 : WRITE (UNIT=output_unit, FMT="(T5,A,/,T5,A,/,T5,A)") &
1721 16 : "The following canonical MO(s) have been associated with the donor state(s)", &
1722 16 : "based on the overlap with the components of a minimal STO basis: ", &
1723 32 : " Spin MO index overlap(sum)"
1724 : END IF
1725 :
1726 64 : ALLOCATE (donor_state%energy_evals(n_states, nspins))
1727 120 : donor_state%energy_evals = 0.0_dp
1728 :
1729 : ! Canonical MO, no change in eigenvalues, only diagonal elements
1730 70 : DO ispin = 1, nspins
1731 38 : CALL get_mo_set(mos(ispin), eigenvalues=mo_evals)
1732 120 : DO i = 1, n_states
1733 50 : donor_state%energy_evals(i, ispin) = mo_evals(my_mos(i, ispin))
1734 :
1735 88 : IF (output_unit > 0) THEN
1736 : WRITE (UNIT=output_unit, FMT="(T46,I4,I11,F17.5)") &
1737 25 : ispin, my_mos(i, ispin), max_overlap(i, ispin)
1738 : END IF
1739 : END DO
1740 : END DO
1741 :
1742 : !either localization of MOs or ROKS, in both cases the MO eigenvalues from the KS
1743 : !digonalization mat have changed
1744 : ELSE
1745 52 : IF (output_unit > 0) THEN
1746 : WRITE (UNIT=output_unit, FMT="(T5,A,/,T5,A,/,T5,A)") &
1747 26 : "The following localized MO(s) have been associated with the donor state(s)", &
1748 26 : "based on the overlap with the components of a minimal STO basis: ", &
1749 52 : " Spin MO index overlap(sum)"
1750 : END IF
1751 :
1752 : ! Loop over the donor states and print
1753 108 : DO ispin = 1, nspins
1754 172 : DO i = 1, n_states
1755 :
1756 : ! Print info
1757 120 : IF (output_unit > 0) THEN
1758 : WRITE (UNIT=output_unit, FMT="(T46,I4,I11,F17.5)") &
1759 32 : ispin, my_mos(i, ispin), max_overlap(i, ispin)
1760 : END IF
1761 : END DO
1762 : END DO
1763 :
1764 : ! MO have been rotated or non-physical ROKS MO eigrenvalues:
1765 : ! => need epsilon_ij = <psi_i|F|psi_j> = sum_{pq} c_{qi}c_{pj} F_{pq}
1766 : ! Note: only have digonal elements by construction
1767 52 : ndo_so = nspins*n_states
1768 52 : CALL cp_fm_create(work_mat, gs_struct)
1769 : CALL cp_fm_struct_create(eval_mat_struct, nrow_global=ndo_so, ncol_global=ndo_so, &
1770 52 : para_env=para_env, context=blacs_env)
1771 52 : CALL cp_fm_create(eval_mat, eval_mat_struct)
1772 156 : ALLOCATE (diag(ndo_so))
1773 :
1774 52 : IF (.NOT. xas_tdp_control%do_roks) THEN
1775 :
1776 100 : ALLOCATE (donor_state%energy_evals(n_states, nspins))
1777 166 : donor_state%energy_evals = 0.0_dp
1778 :
1779 : ! Compute gs_coeff^T * matrix_ks * gs_coeff to get the epsilon_ij matrix
1780 104 : DO ispin = 1, nspins
1781 54 : CALL cp_dbcsr_sm_fm_multiply(matrix_ks(ispin)%matrix, gs_coeffs, work_mat, ncol=ndo_so)
1782 54 : CALL parallel_gemm('T', 'N', ndo_so, ndo_so, nao, 1.0_dp, gs_coeffs, work_mat, 0.0_dp, eval_mat)
1783 :
1784 : ! Put the epsilon_ii into the donor_state. No off-diagonal element because of subset diag
1785 54 : CALL cp_fm_get_diag(eval_mat, diag)
1786 166 : donor_state%energy_evals(:, ispin) = diag((ispin - 1)*n_states + 1:ispin*n_states)
1787 :
1788 : END DO
1789 :
1790 : ELSE
1791 : ! If ROKS, slightly different procedure => 2 KS matrices but one type of MOs
1792 2 : ALLOCATE (donor_state%energy_evals(n_states, 2))
1793 10 : donor_state%energy_evals = 0.0_dp
1794 :
1795 : ! Compute gs_coeff^T * matrix_ks * gs_coeff to get the epsilon_ij matrix
1796 6 : DO ispin = 1, 2
1797 4 : CALL cp_dbcsr_sm_fm_multiply(matrix_ks(ispin)%matrix, gs_coeffs, work_mat, ncol=ndo_so)
1798 4 : CALL parallel_gemm('T', 'N', ndo_so, ndo_so, nao, 1.0_dp, gs_coeffs, work_mat, 0.0_dp, eval_mat)
1799 :
1800 4 : CALL cp_fm_get_diag(eval_mat, diag)
1801 10 : donor_state%energy_evals(:, ispin) = diag(:)
1802 :
1803 : END DO
1804 :
1805 2 : DEALLOCATE (diag)
1806 : END IF
1807 :
1808 : ! Clean-up
1809 52 : CALL cp_fm_release(work_mat)
1810 52 : CALL cp_fm_release(eval_mat)
1811 156 : CALL cp_fm_struct_release(eval_mat_struct)
1812 :
1813 : END IF ! do_localize and/or ROKS
1814 :
1815 : ! Allocate and initialize GW2X corrected IPs as energy_evals
1816 336 : ALLOCATE (donor_state%gw2x_evals(SIZE(donor_state%energy_evals, 1), SIZE(donor_state%energy_evals, 2)))
1817 296 : donor_state%gw2x_evals(:, :) = donor_state%energy_evals(:, :)
1818 :
1819 : ! Clean-up
1820 84 : CALL cp_fm_struct_release(gs_struct)
1821 84 : DEALLOCATE (first_sgf)
1822 :
1823 84 : IF (output_unit > 0) WRITE (UNIT=output_unit, FMT="(T5,A)") " "
1824 :
1825 178 : DO ispin = 1, nspins
1826 178 : IF (output_unit > 0) THEN
1827 : WRITE (UNIT=output_unit, FMT="(T5,A,I1,A,F7.5,A,I4)") &
1828 47 : "The next best overlap for spin ", ispin, " is ", next_best_overlap(ispin), &
1829 94 : " for MO with index ", next_best_overlap_ind(ispin)
1830 : END IF
1831 : END DO
1832 84 : IF (output_unit > 0) WRITE (UNIT=output_unit, FMT="(T5,A)") " "
1833 :
1834 : ELSE
1835 0 : CPABORT("A core donor state could not be assigned MO(s). Increasing NSEARCH might help.")
1836 : END IF
1837 :
1838 336 : END SUBROUTINE assign_mos_to_donor_state
1839 :
1840 : ! **************************************************************************************************
1841 : !> \brief Compute the centers and spreads of (core) MOs using the Berry phase operator
1842 : !> \param xas_tdp_env ...
1843 : !> \param xas_tdp_control ...
1844 : !> \param qs_env ...
1845 : !> \note xas_tdp_env%qs_loc_env is used and modified. OK since no localization done after this
1846 : !> subroutine is used.
1847 : ! **************************************************************************************************
1848 96 : SUBROUTINE find_mo_centers(xas_tdp_env, xas_tdp_control, qs_env)
1849 :
1850 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1851 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1852 : TYPE(qs_environment_type), POINTER :: qs_env
1853 :
1854 : INTEGER :: dim_op, i, ispin, j, n_centers, nao, &
1855 : nspins
1856 : REAL(dp), DIMENSION(6) :: weights
1857 : TYPE(cell_type), POINTER :: cell
1858 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
1859 : TYPE(cp_fm_struct_type), POINTER :: tmp_fm_struct
1860 : TYPE(cp_fm_type) :: opvec
1861 96 : TYPE(cp_fm_type), ALLOCATABLE, DIMENSION(:, :) :: zij_fm_set
1862 96 : TYPE(cp_fm_type), DIMENSION(:), POINTER :: moloc_coeff
1863 : TYPE(cp_fm_type), POINTER :: vectors
1864 96 : TYPE(dbcsr_p_type), DIMENSION(:, :), POINTER :: op_sm_set
1865 : TYPE(mp_para_env_type), POINTER :: para_env
1866 : TYPE(qs_loc_env_type), POINTER :: qs_loc_env
1867 : TYPE(section_vals_type), POINTER :: print_loc_section, prog_run_info
1868 :
1869 96 : NULLIFY (qs_loc_env, cell, print_loc_section, op_sm_set, moloc_coeff, vectors)
1870 96 : NULLIFY (tmp_fm_struct, para_env, blacs_env, prog_run_info)
1871 :
1872 : ! Initialization
1873 96 : print_loc_section => xas_tdp_control%print_loc_subsection
1874 96 : n_centers = xas_tdp_control%n_search
1875 96 : CALL get_qs_env(qs_env=qs_env, para_env=para_env, blacs_env=blacs_env, cell=cell)
1876 :
1877 : ! Set print option to debug to keep clean output file
1878 96 : prog_run_info => section_vals_get_subs_vals(print_loc_section, "PROGRAM_RUN_INFO")
1879 : CALL section_vals_val_set(prog_run_info, keyword_name="_SECTION_PARAMETERS_", &
1880 96 : i_val=debug_print_level)
1881 :
1882 : ! Re-initialize the qs_loc_env to get the current MOs. Use force_loc because needed for centers
1883 96 : CALL reinit_qs_loc_env(xas_tdp_env%qs_loc_env, n_centers, xas_tdp_control%do_uks, qs_env)
1884 96 : qs_loc_env => xas_tdp_env%qs_loc_env
1885 :
1886 : ! Get what we need from the qs_lovc_env
1887 : CALL get_qs_loc_env(qs_loc_env=qs_loc_env, weights=weights, op_sm_set=op_sm_set, &
1888 96 : moloc_coeff=moloc_coeff)
1889 :
1890 : ! Prepare for zij
1891 96 : vectors => moloc_coeff(1)
1892 96 : CALL cp_fm_get_info(vectors, nrow_global=nao)
1893 96 : CALL cp_fm_create(opvec, vectors%matrix_struct)
1894 :
1895 : CALL cp_fm_struct_create(tmp_fm_struct, para_env=para_env, context=blacs_env, &
1896 96 : ncol_global=n_centers, nrow_global=n_centers)
1897 :
1898 96 : IF (cell%orthorhombic) THEN
1899 : dim_op = 3
1900 : ELSE
1901 0 : dim_op = 6
1902 : END IF
1903 1056 : ALLOCATE (zij_fm_set(2, dim_op))
1904 384 : DO i = 1, dim_op
1905 960 : DO j = 1, 2
1906 864 : CALL cp_fm_create(zij_fm_set(j, i), tmp_fm_struct)
1907 : END DO
1908 : END DO
1909 :
1910 : ! If spin-unrestricted, need to go spin by spin
1911 96 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
1912 :
1913 202 : DO ispin = 1, nspins
1914 : ! zij computation, copied from qs_loc_methods:optimize_loc_berry
1915 106 : vectors => moloc_coeff(ispin)
1916 424 : DO i = 1, dim_op
1917 1060 : DO j = 1, 2
1918 636 : CALL cp_fm_set_all(zij_fm_set(j, i), 0.0_dp)
1919 636 : CALL cp_dbcsr_sm_fm_multiply(op_sm_set(j, i)%matrix, vectors, opvec, ncol=n_centers)
1920 : CALL parallel_gemm("T", "N", n_centers, n_centers, nao, 1.0_dp, vectors, opvec, 0.0_dp, &
1921 954 : zij_fm_set(j, i))
1922 : END DO
1923 : END DO
1924 :
1925 : ! Compute centers (and spread)
1926 : CALL centers_spreads_berry(qs_loc_env=qs_loc_env, zij=zij_fm_set, nmoloc=n_centers, &
1927 : cell=cell, weights=weights, ispin=ispin, &
1928 202 : print_loc_section=print_loc_section, only_initial_out=.TRUE.)
1929 : END DO !ispins
1930 :
1931 : ! Clean-up
1932 96 : CALL cp_fm_release(opvec)
1933 96 : CALL cp_fm_struct_release(tmp_fm_struct)
1934 96 : CALL cp_fm_release(zij_fm_set)
1935 :
1936 : ! Make sure we leave with the correct do_loc value
1937 96 : qs_loc_env%do_localize = xas_tdp_control%do_loc
1938 :
1939 288 : END SUBROUTINE find_mo_centers
1940 :
1941 : ! **************************************************************************************************
1942 : !> \brief Prints the MO to donor_state assocaition with overlap and Mulliken population analysis
1943 : !> \param xas_tdp_env ...
1944 : !> \param xas_tdp_control ...
1945 : !> \param qs_env ...
1946 : !> \note Called only in case of CHECK_ONLY run
1947 : ! **************************************************************************************************
1948 0 : SUBROUTINE print_checks(xas_tdp_env, xas_tdp_control, qs_env)
1949 :
1950 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1951 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1952 : TYPE(qs_environment_type), POINTER :: qs_env
1953 :
1954 : CHARACTER(LEN=default_string_length) :: kind_name
1955 : INTEGER :: current_state_index, iat, iatom, ikind, &
1956 : istate, output_unit, tmp_index
1957 0 : INTEGER, DIMENSION(:), POINTER :: atoms_of_kind
1958 0 : TYPE(atomic_kind_type), DIMENSION(:), POINTER :: atomic_kind_set
1959 : TYPE(donor_state_type), POINTER :: current_state
1960 :
1961 0 : NULLIFY (atomic_kind_set, atoms_of_kind, current_state)
1962 :
1963 0 : output_unit = cp_logger_get_default_io_unit()
1964 :
1965 0 : IF (output_unit > 0) THEN
1966 : WRITE (output_unit, "(/,T3,A,/,T3,A,/,T3,A)") &
1967 0 : "# Check the donor states for their quality. They need to have a well defined type ", &
1968 0 : " (1s, 2s, etc) which is indicated by the overlap. They also need to be localized, ", &
1969 0 : " for which the Mulliken population analysis is one indicator (must be close to 1.0)"
1970 : END IF
1971 :
1972 : ! Loop over the donor states (as in the main xas_tdp loop)
1973 0 : CALL get_qs_env(qs_env=qs_env, atomic_kind_set=atomic_kind_set)
1974 0 : current_state_index = 1
1975 :
1976 : !loop over atomic kinds
1977 0 : DO ikind = 1, SIZE(atomic_kind_set)
1978 :
1979 : CALL get_atomic_kind(atomic_kind=atomic_kind_set(ikind), name=kind_name, &
1980 0 : atom_list=atoms_of_kind)
1981 :
1982 0 : IF (.NOT. ANY(xas_tdp_env%ex_kind_indices == ikind)) CYCLE
1983 :
1984 : !loop over atoms of kind
1985 0 : DO iat = 1, SIZE(atoms_of_kind)
1986 0 : iatom = atoms_of_kind(iat)
1987 :
1988 0 : IF (.NOT. ANY(xas_tdp_env%ex_atom_indices == iatom)) CYCLE
1989 0 : tmp_index = locate(xas_tdp_env%ex_atom_indices, iatom)
1990 :
1991 : !loop over states of excited atom
1992 0 : DO istate = 1, SIZE(xas_tdp_env%state_types, 1)
1993 :
1994 0 : IF (xas_tdp_env%state_types(istate, tmp_index) == xas_not_excited) CYCLE
1995 :
1996 0 : current_state => xas_tdp_env%donor_states(current_state_index)
1997 : CALL set_donor_state(current_state, at_index=iatom, &
1998 : at_symbol=kind_name, kind_index=ikind, &
1999 0 : state_type=xas_tdp_env%state_types(istate, tmp_index))
2000 :
2001 0 : IF (output_unit > 0) THEN
2002 : WRITE (output_unit, "(/,T4,A,A2,A,I4,A,A,A)") &
2003 0 : "-Donor state of type ", xas_tdp_env%state_type_char(current_state%state_type), &
2004 0 : " for atom", current_state%at_index, " of kind ", TRIM(current_state%at_symbol), ":"
2005 : END IF
2006 :
2007 : !Assign the MOs and perform Mulliken
2008 0 : CALL assign_mos_to_donor_state(current_state, xas_tdp_env, xas_tdp_control, qs_env)
2009 0 : CALL perform_mulliken_on_donor_state(current_state, qs_env)
2010 :
2011 0 : current_state_index = current_state_index + 1
2012 0 : NULLIFY (current_state)
2013 :
2014 : END DO !istate
2015 : END DO !iat
2016 : END DO !ikind
2017 :
2018 0 : IF (output_unit > 0) THEN
2019 : WRITE (output_unit, "(/,T5,A)") &
2020 0 : "Use LOCALIZE and/or increase N_SEARCH for better results, if so required."
2021 : END IF
2022 :
2023 0 : END SUBROUTINE print_checks
2024 :
2025 : ! **************************************************************************************************
2026 : !> \brief Computes the required multipole moment in the length representation for a given atom
2027 : !> \param iatom index of the given atom
2028 : !> \param xas_tdp_env ...
2029 : !> \param xas_tdp_control ...
2030 : !> \param qs_env ...
2031 : !> \note Assumes that wither dipole or quadrupole in length rep is required
2032 : ! **************************************************************************************************
2033 28 : SUBROUTINE compute_lenrep_multipole(iatom, xas_tdp_env, xas_tdp_control, qs_env)
2034 :
2035 : INTEGER, INTENT(IN) :: iatom
2036 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2037 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2038 : TYPE(qs_environment_type), POINTER :: qs_env
2039 :
2040 : INTEGER :: i, order
2041 : REAL(dp), DIMENSION(3) :: rc
2042 28 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: work
2043 28 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
2044 :
2045 28 : NULLIFY (work, particle_set)
2046 :
2047 28 : CALL get_qs_env(qs_env, particle_set=particle_set)
2048 112 : rc = particle_set(iatom)%r
2049 :
2050 280 : ALLOCATE (work(9))
2051 28 : IF (xas_tdp_control%dipole_form == xas_dip_len) THEN
2052 112 : DO i = 1, 3
2053 84 : CALL dbcsr_set(xas_tdp_env%dipmat(i)%matrix, 0.0_dp)
2054 112 : work(i)%matrix => xas_tdp_env%dipmat(i)%matrix
2055 : END DO
2056 28 : order = 1
2057 : END IF
2058 28 : IF (xas_tdp_control%do_quad) THEN
2059 0 : DO i = 1, 6
2060 0 : CALL dbcsr_set(xas_tdp_env%quadmat(i)%matrix, 0.0_dp)
2061 0 : work(3 + i)%matrix => xas_tdp_env%quadmat(i)%matrix
2062 : END DO
2063 0 : order = 2
2064 0 : IF (xas_tdp_control%dipole_form == xas_dip_vel) order = -2
2065 : END IF
2066 :
2067 : !enforce minimum image to avoid PBCs related issues, ok because localized densities
2068 28 : CALL rRc_xyz_ao(work, qs_env, rc, order=order, minimum_image=.TRUE.)
2069 28 : DEALLOCATE (work)
2070 :
2071 28 : END SUBROUTINE compute_lenrep_multipole
2072 :
2073 : ! **************************************************************************************************
2074 : !> \brief Computes the oscillator strength based on the dipole moment (velocity or length rep) for
2075 : !> all available excitation energies and store the results in the donor_state. There is no
2076 : !> triplet dipole in the spin-restricted ground state.
2077 : !> \param donor_state the donor state which is excited
2078 : !> \param xas_tdp_control ...
2079 : !> \param xas_tdp_env ...
2080 : !> \note The oscillator strength is a scalar: osc_str = 2/(3*omega)*(dipole_v)^2 in the velocity rep
2081 : !> or : osc_str = 2/3*omega*(dipole_r)^2 in the length representation
2082 : !> The formulae for the dipoles come from the trace of the dipole operator with the transition
2083 : !> densities, i.e. what we get from solving the xas_tdp problem. Same procedure with or wo TDA
2084 : ! **************************************************************************************************
2085 72 : SUBROUTINE compute_dipole_fosc(donor_state, xas_tdp_control, xas_tdp_env)
2086 :
2087 : TYPE(donor_state_type), POINTER :: donor_state
2088 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2089 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2090 :
2091 : CHARACTER(len=*), PARAMETER :: routineN = 'compute_dipole_fosc'
2092 :
2093 : INTEGER :: handle, iosc, j, nao, ndo_mo, ndo_so, &
2094 : ngs, nosc, nspins
2095 : LOGICAL :: do_sc, do_sg
2096 : REAL(dp) :: alpha_xyz, beta_xyz, osc_xyz, pref
2097 72 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: alpha_contr, beta_contr, tot_contr
2098 72 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: dip_block
2099 72 : REAL(dp), DIMENSION(:), POINTER :: lr_evals
2100 72 : REAL(dp), DIMENSION(:, :), POINTER :: alpha_osc, beta_osc, osc_str
2101 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2102 : TYPE(cp_fm_struct_type), POINTER :: col_struct, mat_struct
2103 : TYPE(cp_fm_type) :: col_work, mat_work
2104 : TYPE(cp_fm_type), POINTER :: lr_coeffs
2105 72 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: dipmat
2106 : TYPE(mp_para_env_type), POINTER :: para_env
2107 :
2108 72 : NULLIFY (dipmat, col_struct, mat_struct, para_env, blacs_env, lr_coeffs)
2109 72 : NULLIFY (lr_evals, osc_str, alpha_osc, beta_osc)
2110 :
2111 72 : CALL timeset(routineN, handle)
2112 :
2113 : ! Initialization
2114 72 : do_sc = xas_tdp_control%do_spin_cons
2115 72 : do_sg = xas_tdp_control%do_singlet
2116 72 : IF (do_sc) THEN
2117 12 : nspins = 2
2118 12 : lr_evals => donor_state%sc_evals
2119 12 : lr_coeffs => donor_state%sc_coeffs
2120 60 : ELSE IF (do_sg) THEN
2121 60 : nspins = 1
2122 60 : lr_evals => donor_state%sg_evals
2123 60 : lr_coeffs => donor_state%sg_coeffs
2124 : ELSE
2125 0 : CPABORT("Dipole oscilaltor strength only for singlets and spin-conserving excitations.")
2126 : END IF
2127 72 : ndo_mo = donor_state%ndo_mo
2128 72 : ndo_so = ndo_mo*nspins
2129 72 : ngs = ndo_so; IF (xas_tdp_control%do_roks) ngs = ndo_mo !in ROKS, same gs coeffs
2130 72 : nosc = SIZE(lr_evals)
2131 360 : ALLOCATE (donor_state%osc_str(nosc, 4), donor_state%alpha_osc(nosc, 4), donor_state%beta_osc(nosc, 4))
2132 72 : osc_str => donor_state%osc_str
2133 72 : alpha_osc => donor_state%alpha_osc
2134 72 : beta_osc => donor_state%beta_osc
2135 4648 : osc_str = 0.0_dp
2136 4648 : alpha_osc = 0.0_dp
2137 4648 : beta_osc = 0.0_dp
2138 72 : dipmat => xas_tdp_env%dipmat
2139 :
2140 : ! do some work matrix initialization
2141 : CALL cp_fm_get_info(donor_state%gs_coeffs, matrix_struct=col_struct, para_env=para_env, &
2142 72 : context=blacs_env, nrow_global=nao)
2143 : CALL cp_fm_struct_create(mat_struct, para_env=para_env, context=blacs_env, &
2144 72 : nrow_global=ndo_so*nosc, ncol_global=ngs)
2145 72 : CALL cp_fm_create(mat_work, mat_struct)
2146 72 : CALL cp_fm_create(col_work, col_struct)
2147 :
2148 576 : ALLOCATE (tot_contr(ndo_mo), dip_block(ndo_so, ngs), alpha_contr(ndo_mo), beta_contr(ndo_mo))
2149 72 : pref = 2.0_dp; IF (do_sc) pref = 1.0_dp !because of singlet definition u = 1/sqrt(2)(c_a+c_b)
2150 :
2151 : ! Looping over cartesian coord
2152 288 : DO j = 1, 3
2153 :
2154 : !Compute dip*gs_coeffs
2155 216 : CALL cp_dbcsr_sm_fm_multiply(dipmat(j)%matrix, donor_state%gs_coeffs, col_work, ncol=ngs)
2156 : !compute lr_coeffs*dip*gs_coeffs
2157 216 : CALL parallel_gemm('T', 'N', ndo_so*nosc, ngs, nao, 1.0_dp, lr_coeffs, col_work, 0.0_dp, mat_work)
2158 :
2159 : !Loop over the excited states
2160 3504 : DO iosc = 1, nosc
2161 :
2162 6720 : tot_contr = 0.0_dp
2163 : CALL cp_fm_get_submatrix(fm=mat_work, target_m=dip_block, start_row=(iosc - 1)*ndo_so + 1, &
2164 3216 : start_col=1, n_rows=ndo_so, n_cols=ngs)
2165 3216 : IF (do_sg) THEN
2166 2448 : tot_contr(:) = get_diag(dip_block)
2167 768 : ELSE IF (do_sc .AND. xas_tdp_control%do_uks) THEN
2168 696 : alpha_contr(:) = get_diag(dip_block(1:ndo_mo, 1:ndo_mo))
2169 696 : beta_contr(:) = get_diag(dip_block(ndo_mo + 1:ndo_so, ndo_mo + 1:ndo_so))
2170 1536 : tot_contr(:) = alpha_contr(:) + beta_contr(:)
2171 : ELSE
2172 : !roks
2173 72 : alpha_contr(:) = get_diag(dip_block(1:ndo_mo, :))
2174 72 : beta_contr(:) = get_diag(dip_block(ndo_mo + 1:ndo_so, :))
2175 144 : tot_contr(:) = alpha_contr(:) + beta_contr(:)
2176 : END IF
2177 :
2178 6720 : osc_xyz = SUM(tot_contr)**2
2179 6720 : alpha_xyz = SUM(alpha_contr)**2
2180 6720 : beta_xyz = SUM(beta_contr)**2
2181 :
2182 3216 : alpha_osc(iosc, 4) = alpha_osc(iosc, 4) + alpha_xyz
2183 3216 : alpha_osc(iosc, j) = alpha_xyz
2184 :
2185 3216 : beta_osc(iosc, 4) = beta_osc(iosc, 4) + beta_xyz
2186 3216 : beta_osc(iosc, j) = beta_xyz
2187 :
2188 3216 : osc_str(iosc, 4) = osc_str(iosc, 4) + osc_xyz
2189 3432 : osc_str(iosc, j) = osc_xyz
2190 :
2191 : END DO !iosc
2192 : END DO !j
2193 :
2194 : !compute the prefactor
2195 360 : DO j = 1, 4
2196 360 : IF (xas_tdp_control%dipole_form == xas_dip_len) THEN
2197 3664 : osc_str(:, j) = pref*2.0_dp/3.0_dp*lr_evals(:)*osc_str(:, j)
2198 3664 : alpha_osc(:, j) = pref*2.0_dp/3.0_dp*lr_evals(:)*alpha_osc(:, j)
2199 3664 : beta_osc(:, j) = pref*2.0_dp/3.0_dp*lr_evals(:)*beta_osc(:, j)
2200 : ELSE
2201 5488 : osc_str(:, j) = pref*2.0_dp/3.0_dp/lr_evals(:)*osc_str(:, j)
2202 5488 : alpha_osc(:, j) = pref*2.0_dp/3.0_dp/lr_evals(:)*alpha_osc(:, j)
2203 5488 : beta_osc(:, j) = pref*2.0_dp/3.0_dp/lr_evals(:)*beta_osc(:, j)
2204 : END IF
2205 : END DO
2206 :
2207 : !clean-up
2208 72 : CALL cp_fm_release(mat_work)
2209 72 : CALL cp_fm_release(col_work)
2210 72 : CALL cp_fm_struct_release(mat_struct)
2211 :
2212 72 : CALL timestop(handle)
2213 :
2214 288 : END SUBROUTINE compute_dipole_fosc
2215 :
2216 : ! **************************************************************************************************
2217 : !> \brief Computes the oscillator strength due to the electric quadrupole moment and store it in
2218 : !> the donor_state (for singlet or spin-conserving)
2219 : !> \param donor_state the donor state which is excited
2220 : !> \param xas_tdp_control ...
2221 : !> \param xas_tdp_env ...
2222 : !> \note Formula: 1/20*a_fine^2*omega^3 * sum_ab (sum_i r_ia*r_ib - 1/3*ri^2*delta_ab)
2223 : ! **************************************************************************************************
2224 0 : SUBROUTINE compute_quadrupole_fosc(donor_state, xas_tdp_control, xas_tdp_env)
2225 :
2226 : TYPE(donor_state_type), POINTER :: donor_state
2227 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2228 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2229 :
2230 : CHARACTER(len=*), PARAMETER :: routineN = 'compute_quadrupole_fosc'
2231 :
2232 : INTEGER :: handle, iosc, j, nao, ndo_mo, ndo_so, &
2233 : ngs, nosc, nspins
2234 : LOGICAL :: do_sc, do_sg
2235 : REAL(dp) :: pref
2236 0 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: tot_contr, trace
2237 0 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: quad_block
2238 0 : REAL(dp), DIMENSION(:), POINTER :: lr_evals, osc_str
2239 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2240 : TYPE(cp_fm_struct_type), POINTER :: col_struct, mat_struct
2241 : TYPE(cp_fm_type) :: col_work, mat_work
2242 : TYPE(cp_fm_type), POINTER :: lr_coeffs
2243 0 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: quadmat
2244 : TYPE(mp_para_env_type), POINTER :: para_env
2245 :
2246 0 : NULLIFY (lr_evals, osc_str, lr_coeffs, col_struct, mat_struct, para_env)
2247 0 : NULLIFY (blacs_env)
2248 :
2249 0 : CALL timeset(routineN, handle)
2250 :
2251 : ! Initialization
2252 0 : do_sc = xas_tdp_control%do_spin_cons
2253 0 : do_sg = xas_tdp_control%do_singlet
2254 0 : IF (do_sc) THEN
2255 0 : nspins = 2
2256 0 : lr_evals => donor_state%sc_evals
2257 0 : lr_coeffs => donor_state%sc_coeffs
2258 0 : ELSE IF (do_sg) THEN
2259 0 : nspins = 1
2260 0 : lr_evals => donor_state%sg_evals
2261 0 : lr_coeffs => donor_state%sg_coeffs
2262 : ELSE
2263 0 : CPABORT("Quadrupole oscillator strengths only for singlet and spin-conserving excitations")
2264 : END IF
2265 0 : ndo_mo = donor_state%ndo_mo
2266 0 : ndo_so = ndo_mo*nspins
2267 0 : ngs = ndo_so; IF (xas_tdp_control%do_roks) ngs = ndo_mo !only alpha do_mo in ROKS
2268 0 : nosc = SIZE(lr_evals)
2269 0 : ALLOCATE (donor_state%quad_osc_str(nosc))
2270 0 : osc_str => donor_state%quad_osc_str
2271 0 : osc_str = 0.0_dp
2272 0 : quadmat => xas_tdp_env%quadmat
2273 :
2274 : !work matrices init
2275 : CALL cp_fm_get_info(donor_state%gs_coeffs, matrix_struct=col_struct, para_env=para_env, &
2276 0 : context=blacs_env, nrow_global=nao)
2277 : CALL cp_fm_struct_create(mat_struct, para_env=para_env, context=blacs_env, &
2278 0 : nrow_global=ndo_so*nosc, ncol_global=ngs)
2279 0 : CALL cp_fm_create(mat_work, mat_struct)
2280 0 : CALL cp_fm_create(col_work, col_struct)
2281 :
2282 0 : ALLOCATE (quad_block(ndo_so, ngs), tot_contr(ndo_mo))
2283 0 : pref = 2.0_dp; IF (do_sc) pref = 1.0_dp !because of singlet definition u = 1/sqrt(2)*...
2284 0 : ALLOCATE (trace(nosc))
2285 0 : trace = 0.0_dp
2286 :
2287 : !Loop over the cartesioan coord :x2, xy, xz, y2, yz, z2
2288 0 : DO j = 1, 6
2289 :
2290 : !Compute quad*gs_coeffs
2291 0 : CALL cp_dbcsr_sm_fm_multiply(quadmat(j)%matrix, donor_state%gs_coeffs, col_work, ncol=ngs)
2292 : !compute lr_coeffs*quadmat*gs_coeffs
2293 0 : CALL parallel_gemm('T', 'N', ndo_so*nosc, ngs, nao, 1.0_dp, lr_coeffs, col_work, 0.0_dp, mat_work)
2294 :
2295 : !Loop over the excited states
2296 0 : DO iosc = 1, nosc
2297 :
2298 0 : tot_contr = 0.0_dp
2299 : CALL cp_fm_get_submatrix(fm=mat_work, target_m=quad_block, start_row=(iosc - 1)*ndo_so + 1, &
2300 0 : start_col=1, n_rows=ndo_so, n_cols=ngs)
2301 :
2302 0 : IF (do_sg) THEN
2303 0 : tot_contr(:) = get_diag(quad_block)
2304 0 : ELSE IF (do_sc .AND. xas_tdp_control%do_uks) THEN
2305 0 : tot_contr(:) = get_diag(quad_block(1:ndo_mo, 1:ndo_mo)) !alpha
2306 0 : tot_contr(:) = tot_contr(:) + get_diag(quad_block(ndo_mo + 1:ndo_so, ndo_mo + 1:ndo_so)) !beta
2307 : ELSE
2308 : !roks
2309 0 : tot_contr(:) = get_diag(quad_block(1:ndo_mo, :)) !alpha
2310 0 : tot_contr(:) = tot_contr(:) + get_diag(quad_block(ndo_mo + 1:ndo_so, :)) !beta
2311 : END IF
2312 :
2313 : !if x2, y2, or z2 direction, need to update the trace (for later)
2314 0 : IF (j == 1 .OR. j == 4 .OR. j == 6) THEN
2315 0 : osc_str(iosc) = osc_str(iosc) + SUM(tot_contr)**2
2316 0 : trace(iosc) = trace(iosc) + SUM(tot_contr)
2317 :
2318 : !if xy, xz or yz, need to count twice the contribution (for yx, zx and zy)
2319 : ELSE
2320 0 : osc_str(iosc) = osc_str(iosc) + 2.0_dp*SUM(tot_contr)**2
2321 : END IF
2322 :
2323 : END DO !iosc
2324 : END DO !j
2325 :
2326 : !compute the prefactor, and remove 1/3*trace^2
2327 0 : osc_str(:) = pref*1._dp/20._dp*a_fine**2*lr_evals(:)**3*(osc_str(:) - 1._dp/3._dp*trace(:)**2)
2328 :
2329 : !clean-up
2330 0 : CALL cp_fm_release(mat_work)
2331 0 : CALL cp_fm_release(col_work)
2332 0 : CALL cp_fm_struct_release(mat_struct)
2333 :
2334 0 : CALL timestop(handle)
2335 :
2336 0 : END SUBROUTINE compute_quadrupole_fosc
2337 :
2338 : ! **************************************************************************************************
2339 : !> \brief Writes the core MOs to excited atoms associations in the main output file
2340 : !> \param xas_tdp_env ...
2341 : !> \param xas_tdp_control ...
2342 : !> \param qs_env ...
2343 : !> \note Look at alpha spin MOs, as we are dealing with core states and alpha/beta MOs are the same
2344 : ! **************************************************************************************************
2345 62 : SUBROUTINE write_mos_to_ex_atoms_association(xas_tdp_env, xas_tdp_control, qs_env)
2346 :
2347 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2348 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2349 : TYPE(qs_environment_type), POINTER :: qs_env
2350 :
2351 : CHARACTER(LEN=default_string_length) :: kind_name
2352 : INTEGER :: at_index, imo, ispin, nmo, nspins, &
2353 : output_unit, tmp_index
2354 : INTEGER, DIMENSION(3) :: perd_init
2355 62 : INTEGER, DIMENSION(:), POINTER :: ex_atom_indices
2356 62 : INTEGER, DIMENSION(:, :, :), POINTER :: mos_of_ex_atoms
2357 : REAL(dp) :: dist, mo_spread
2358 : REAL(dp), DIMENSION(3) :: at_pos, r_ac, wfn_center
2359 : TYPE(cell_type), POINTER :: cell
2360 62 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
2361 :
2362 62 : NULLIFY (cell, particle_set, mos_of_ex_atoms, ex_atom_indices)
2363 :
2364 124 : output_unit = cp_logger_get_default_io_unit()
2365 :
2366 62 : IF (output_unit > 0) THEN
2367 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/,T3,A,/,T3,A)") &
2368 31 : " Associated Associated Distance to MO spread (Ang^2)", &
2369 31 : "Spin MO index atom index atom kind MO center (Ang) -w_i ln(|z_ij|^2)", &
2370 62 : "---------------------------------------------------------------------------------"
2371 : END IF
2372 :
2373 : ! Initialization
2374 62 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
2375 62 : mos_of_ex_atoms => xas_tdp_env%mos_of_ex_atoms
2376 62 : ex_atom_indices => xas_tdp_env%ex_atom_indices
2377 62 : nmo = xas_tdp_control%n_search
2378 62 : CALL get_qs_env(qs_env=qs_env, particle_set=particle_set, cell=cell)
2379 :
2380 : ! because the use of Berry's phase operator implies PBCs
2381 248 : perd_init = cell%perd
2382 248 : cell%perd = 1
2383 :
2384 : ! Retrieving all the info for each MO and spin
2385 342 : DO imo = 1, nmo
2386 640 : DO ispin = 1, nspins
2387 :
2388 : ! each Mo is associated to at most one atom (only 1 in array of -1)
2389 810 : IF (ANY(mos_of_ex_atoms(imo, :, ispin) == 1)) THEN
2390 308 : tmp_index = MAXLOC(mos_of_ex_atoms(imo, :, ispin), 1)
2391 140 : at_index = ex_atom_indices(tmp_index)
2392 140 : kind_name = particle_set(at_index)%atomic_kind%name
2393 :
2394 560 : at_pos = particle_set(at_index)%r
2395 560 : wfn_center = xas_tdp_env%qs_loc_env%localized_wfn_control%centers_set(ispin)%array(1:3, imo)
2396 140 : r_ac = pbc(at_pos, wfn_center, cell)
2397 560 : dist = NORM2(r_ac)
2398 : ! convert distance from a.u. to Angstrom
2399 140 : dist = dist*angstrom
2400 :
2401 140 : mo_spread = xas_tdp_env%qs_loc_env%localized_wfn_control%centers_set(ispin)%array(4, imo)
2402 140 : mo_spread = mo_spread*angstrom*angstrom
2403 :
2404 140 : IF (output_unit > 0) THEN
2405 : WRITE (UNIT=output_unit, FMT="(T3,I4,I10,I14,A14,ES19.3,ES20.3)") &
2406 70 : ispin, imo, at_index, TRIM(kind_name), dist, mo_spread
2407 : END IF
2408 :
2409 : END IF
2410 : END DO !ispin
2411 : END DO !imo
2412 :
2413 62 : IF (output_unit > 0) THEN
2414 : WRITE (UNIT=output_unit, FMT="(T3,A,/)") &
2415 31 : "---------------------------------------------------------------------------------"
2416 : END IF
2417 :
2418 : ! Go back to initial BCs
2419 248 : cell%perd = perd_init
2420 :
2421 62 : END SUBROUTINE write_mos_to_ex_atoms_association
2422 :
2423 : ! **************************************************************************************************
2424 : !> \brief Performs Mulliken population analysis for the MO(s) of a donor_state_type so that user
2425 : !> can verify it is indeed a core state
2426 : !> \param donor_state ...
2427 : !> \param qs_env ...
2428 : !> \note This is a specific case of Mulliken analysis. In general one computes sum_i (SP)_ii, where
2429 : !> i labels the basis function centered on the atom of interest. For a specific MO with index
2430 : !> j, one need to compute sum_{ik} c_{ij} S_{ik} c_{kj}, k = 1,nao
2431 : ! **************************************************************************************************
2432 84 : SUBROUTINE perform_mulliken_on_donor_state(donor_state, qs_env)
2433 : TYPE(donor_state_type), POINTER :: donor_state
2434 : TYPE(qs_environment_type), POINTER :: qs_env
2435 :
2436 : INTEGER :: at_index, i, ispin, nao, natom, ndo_mo, &
2437 : ndo_so, nsgf, nspins, output_unit
2438 84 : INTEGER, DIMENSION(:), POINTER :: first_sgf, last_sgf
2439 84 : INTEGER, DIMENSION(:, :), POINTER :: mo_indices
2440 84 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: mul_pop, pop_mat
2441 84 : REAL(dp), DIMENSION(:, :), POINTER :: work_array
2442 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2443 : TYPE(cp_fm_struct_type), POINTER :: col_vect_struct
2444 : TYPE(cp_fm_type) :: work_vect
2445 : TYPE(cp_fm_type), POINTER :: gs_coeffs
2446 84 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_s
2447 : TYPE(mp_para_env_type), POINTER :: para_env
2448 84 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
2449 84 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
2450 :
2451 84 : NULLIFY (mo_indices, qs_kind_set, particle_set, first_sgf, work_array)
2452 84 : NULLIFY (matrix_s, para_env, blacs_env, col_vect_struct, last_sgf)
2453 :
2454 : ! Initialization
2455 84 : at_index = donor_state%at_index
2456 84 : mo_indices => donor_state%mo_indices
2457 84 : ndo_mo = donor_state%ndo_mo
2458 84 : gs_coeffs => donor_state%gs_coeffs
2459 168 : output_unit = cp_logger_get_default_io_unit()
2460 84 : nspins = 1; IF (SIZE(mo_indices, 2) == 2) nspins = 2
2461 84 : ndo_so = ndo_mo*nspins
2462 336 : ALLOCATE (mul_pop(ndo_mo, nspins))
2463 292 : mul_pop = 0.0_dp
2464 :
2465 : CALL get_qs_env(qs_env=qs_env, particle_set=particle_set, qs_kind_set=qs_kind_set, &
2466 84 : para_env=para_env, blacs_env=blacs_env, matrix_s=matrix_s)
2467 84 : CALL cp_fm_get_info(gs_coeffs, nrow_global=nao, matrix_struct=col_vect_struct)
2468 :
2469 84 : natom = SIZE(particle_set, 1)
2470 252 : ALLOCATE (first_sgf(natom))
2471 168 : ALLOCATE (last_sgf(natom))
2472 :
2473 84 : CALL get_particle_set(particle_set, qs_kind_set, first_sgf=first_sgf, last_sgf=last_sgf)
2474 84 : nsgf = last_sgf(at_index) - first_sgf(at_index) + 1
2475 :
2476 84 : CALL cp_fm_create(work_vect, col_vect_struct)
2477 :
2478 : ! Take the product of S*coeffs
2479 84 : CALL cp_dbcsr_sm_fm_multiply(matrix_s(1)%matrix, gs_coeffs, work_vect, ncol=ndo_so)
2480 :
2481 : ! Only consider the product coeffs^T * S * coeffs on the atom of interest
2482 336 : ALLOCATE (work_array(nsgf, ndo_so))
2483 336 : ALLOCATE (pop_mat(ndo_so, ndo_so))
2484 :
2485 : CALL cp_fm_get_submatrix(fm=work_vect, target_m=work_array, start_row=first_sgf(at_index), &
2486 84 : start_col=1, n_rows=nsgf, n_cols=ndo_so, transpose=.FALSE.)
2487 :
2488 : CALL dgemm('T', 'N', ndo_so, ndo_so, nsgf, 1.0_dp, donor_state%contract_coeffs, nsgf, &
2489 84 : work_array, nsgf, 0.0_dp, pop_mat, ndo_so)
2490 :
2491 : ! The Mullikan population for the MOs in on the diagonal.
2492 178 : DO ispin = 1, nspins
2493 292 : DO i = 1, ndo_mo
2494 208 : mul_pop(i, ispin) = pop_mat((ispin - 1)*ndo_mo + i, (ispin - 1)*ndo_mo + i)
2495 : END DO
2496 : END DO
2497 :
2498 : ! Printing in main output file
2499 84 : IF (output_unit > 0) THEN
2500 : WRITE (UNIT=output_unit, FMT="(T5,A,/,T5,A)") &
2501 42 : "Mulliken population analysis retricted to the associated MO(s) yields: ", &
2502 84 : " Spin MO index charge"
2503 89 : DO ispin = 1, nspins
2504 146 : DO i = 1, ndo_mo
2505 : WRITE (UNIT=output_unit, FMT="(T51,I4,I10,F11.3)") &
2506 104 : ispin, mo_indices(i, ispin), mul_pop(i, ispin)
2507 : END DO
2508 : END DO
2509 : END IF
2510 :
2511 : ! Clean-up
2512 84 : DEALLOCATE (first_sgf, last_sgf, work_array)
2513 84 : CALL cp_fm_release(work_vect)
2514 :
2515 336 : END SUBROUTINE perform_mulliken_on_donor_state
2516 :
2517 : ! **************************************************************************************************
2518 : !> \brief write the PDOS wrt the LR-orbitals for the current donor_state and/or the CUBES files
2519 : !> \param ex_type the excitation type: singlet, triplet, spin-conserving, etc
2520 : !> \param donor_state ...
2521 : !> \param xas_tdp_env ...
2522 : !> \param xas_tdp_section ...
2523 : !> \param qs_env ...
2524 : ! **************************************************************************************************
2525 90 : SUBROUTINE xas_tdp_post(ex_type, donor_state, xas_tdp_env, xas_tdp_section, qs_env)
2526 :
2527 : INTEGER, INTENT(IN) :: ex_type
2528 : TYPE(donor_state_type), POINTER :: donor_state
2529 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2530 : TYPE(section_vals_type), POINTER :: xas_tdp_section
2531 : TYPE(qs_environment_type), POINTER :: qs_env
2532 :
2533 : CHARACTER(len=*), PARAMETER :: routineN = 'xas_tdp_post'
2534 :
2535 : CHARACTER(len=default_string_length) :: domo, domon, excite, pos, xas_mittle
2536 : INTEGER :: ex_state_idx, handle, ic, ido_mo, imo, irep, ispin, n_dependent, n_rep, nao, &
2537 : ncubes, ndo_mo, ndo_so, nlumo, nmo, nspins, output_unit
2538 78 : INTEGER, DIMENSION(:), POINTER :: bounds, list, state_list
2539 : LOGICAL :: append_cube, do_cubes, do_pdos, &
2540 : do_wfn_restart
2541 78 : REAL(dp), DIMENSION(:), POINTER :: lr_evals
2542 78 : REAL(dp), DIMENSION(:, :), POINTER :: centers
2543 78 : TYPE(atomic_kind_type), DIMENSION(:), POINTER :: atomic_kind_set
2544 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2545 : TYPE(cp_fm_struct_type), POINTER :: fm_struct, mo_struct
2546 : TYPE(cp_fm_type) :: mo_coeff, work_fm
2547 : TYPE(cp_fm_type), POINTER :: lr_coeffs
2548 : TYPE(cp_logger_type), POINTER :: logger
2549 78 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_s
2550 78 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
2551 : TYPE(mo_set_type), POINTER :: mo_set
2552 : TYPE(mp_para_env_type), POINTER :: para_env
2553 78 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
2554 78 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
2555 : TYPE(section_vals_type), POINTER :: print_key
2556 :
2557 78 : NULLIFY (atomic_kind_set, particle_set, qs_kind_set, mo_set, lr_evals, lr_coeffs)
2558 78 : NULLIFY (mo_struct, para_env, blacs_env, fm_struct, matrix_s, print_key, logger)
2559 78 : NULLIFY (bounds, state_list, list, mos)
2560 :
2561 : !Tests on what to do
2562 156 : logger => cp_get_default_logger()
2563 78 : do_pdos = .FALSE.; do_cubes = .FALSE.; do_wfn_restart = .FALSE.
2564 :
2565 78 : IF (BTEST(cp_print_key_should_output(logger%iter_info, xas_tdp_section, &
2566 2 : "PRINT%PDOS"), cp_p_file)) do_pdos = .TRUE.
2567 :
2568 78 : IF (BTEST(cp_print_key_should_output(logger%iter_info, xas_tdp_section, &
2569 2 : "PRINT%CUBES"), cp_p_file)) do_cubes = .TRUE.
2570 :
2571 78 : IF (BTEST(cp_print_key_should_output(logger%iter_info, xas_tdp_section, &
2572 2 : "PRINT%RESTART_WFN"), cp_p_file)) do_wfn_restart = .TRUE.
2573 :
2574 78 : IF (.NOT. (do_pdos .OR. do_cubes .OR. do_wfn_restart)) RETURN
2575 :
2576 4 : CALL timeset(routineN, handle)
2577 :
2578 : !Initialization
2579 : CALL get_qs_env(qs_env, atomic_kind_set=atomic_kind_set, particle_set=particle_set, &
2580 : qs_kind_set=qs_kind_set, para_env=para_env, blacs_env=blacs_env, &
2581 4 : matrix_s=matrix_s, mos=mos)
2582 :
2583 4 : SELECT CASE (ex_type)
2584 : CASE (tddfpt_spin_cons)
2585 0 : lr_evals => donor_state%sc_evals
2586 0 : lr_coeffs => donor_state%sc_coeffs
2587 0 : nspins = 2
2588 0 : excite = "spincons"
2589 : CASE (tddfpt_spin_flip)
2590 0 : lr_evals => donor_state%sf_evals
2591 0 : lr_coeffs => donor_state%sf_coeffs
2592 0 : nspins = 2
2593 0 : excite = "spinflip"
2594 : CASE (tddfpt_singlet)
2595 4 : lr_evals => donor_state%sg_evals
2596 4 : lr_coeffs => donor_state%sg_coeffs
2597 4 : nspins = 1
2598 4 : excite = "singlet"
2599 : CASE (tddfpt_triplet)
2600 0 : lr_evals => donor_state%tp_evals
2601 0 : lr_coeffs => donor_state%tp_coeffs
2602 0 : nspins = 1
2603 4 : excite = "triplet"
2604 : END SELECT
2605 :
2606 8 : SELECT CASE (donor_state%state_type)
2607 : CASE (xas_1s_type)
2608 4 : domo = "1s"
2609 : CASE (xas_2s_type)
2610 0 : domo = "2s"
2611 : CASE (xas_2p_type)
2612 4 : domo = "2p"
2613 : END SELECT
2614 :
2615 4 : ndo_mo = donor_state%ndo_mo
2616 4 : ndo_so = ndo_mo*nspins
2617 4 : nmo = SIZE(lr_evals)
2618 4 : CALL dbcsr_get_info(matrix_s(1)%matrix, nfullrows_total=nao)
2619 :
2620 : CALL cp_fm_struct_create(mo_struct, context=blacs_env, para_env=para_env, &
2621 4 : nrow_global=nao, ncol_global=nmo)
2622 4 : CALL cp_fm_create(mo_coeff, mo_struct)
2623 :
2624 : !Dump the TDDFT excited state AMEW wavefunction into a file for restart in RTP
2625 4 : IF (do_wfn_restart) THEN
2626 2 : BLOCK
2627 6 : TYPE(mo_set_type), DIMENSION(2) :: restart_mos
2628 2 : IF (.NOT. (nspins == 1 .AND. donor_state%state_type == xas_1s_type)) THEN
2629 0 : CPABORT("RESTART.wfn file only available for RKS K-edge XAS spectroscopy")
2630 : END IF
2631 :
2632 2 : CALL section_vals_val_get(xas_tdp_section, "PRINT%RESTART_WFN%EXCITED_STATE_INDEX", n_rep_val=n_rep)
2633 :
2634 4 : DO irep = 1, n_rep
2635 : CALL section_vals_val_get(xas_tdp_section, "PRINT%RESTART_WFN%EXCITED_STATE_INDEX", &
2636 2 : i_rep_val=irep, i_val=ex_state_idx)
2637 2 : CPASSERT(ex_state_idx <= SIZE(lr_evals))
2638 :
2639 6 : DO ispin = 1, 2
2640 4 : CALL duplicate_mo_set(restart_mos(ispin), mos(1))
2641 : ! Set the new occupation number in the case of spin-independent based calculaltion since the restart is spin-depedent
2642 4 : IF (SIZE(mos) == 1) &
2643 26 : restart_mos(ispin)%occupation_numbers = mos(1)%occupation_numbers/2
2644 : END DO
2645 :
2646 : CALL cp_fm_to_fm_submat(msource=lr_coeffs, mtarget=restart_mos(1)%mo_coeff, nrow=nao, &
2647 : ncol=1, s_firstrow=1, s_firstcol=ex_state_idx, t_firstrow=1, &
2648 2 : t_firstcol=donor_state%mo_indices(1, 1))
2649 :
2650 : xas_mittle = 'xasat'//TRIM(ADJUSTL(cp_to_string(donor_state%at_index)))//'_'//TRIM(domo)// &
2651 2 : '_'//TRIM(excite)//'_idx'//TRIM(ADJUSTL(cp_to_string(ex_state_idx)))
2652 : output_unit = cp_print_key_unit_nr(logger, xas_tdp_section, "PRINT%RESTART_WFN", &
2653 : extension=".wfn", file_status="REPLACE", &
2654 : file_action="WRITE", file_form="UNFORMATTED", &
2655 2 : middle_name=xas_mittle)
2656 :
2657 : CALL write_mo_set_low(restart_mos, particle_set=particle_set, &
2658 2 : qs_kind_set=qs_kind_set, ires=output_unit)
2659 :
2660 2 : CALL cp_print_key_finished_output(output_unit, logger, xas_tdp_section, "PRINT%RESTART_WFN")
2661 :
2662 10 : DO ispin = 1, 2
2663 6 : CALL deallocate_mo_set(restart_mos(ispin))
2664 : END DO
2665 : END DO
2666 : END BLOCK
2667 : END IF
2668 :
2669 : !PDOS related stuff
2670 4 : IF (do_pdos) THEN
2671 :
2672 : !If S^0.5 not yet stored, compute it once and for all
2673 2 : IF (.NOT. ASSOCIATED(xas_tdp_env%matrix_shalf) .AND. do_pdos) THEN
2674 : CALL cp_fm_struct_create(fm_struct, context=blacs_env, para_env=para_env, &
2675 2 : nrow_global=nao, ncol_global=nao)
2676 2 : ALLOCATE (xas_tdp_env%matrix_shalf)
2677 2 : CALL cp_fm_create(xas_tdp_env%matrix_shalf, fm_struct)
2678 2 : CALL cp_fm_create(work_fm, fm_struct)
2679 :
2680 2 : CALL copy_dbcsr_to_fm(matrix_s(1)%matrix, xas_tdp_env%matrix_shalf)
2681 2 : CALL cp_fm_power(xas_tdp_env%matrix_shalf, work_fm, 0.5_dp, EPSILON(0.0_dp), n_dependent)
2682 :
2683 2 : CALL cp_fm_release(work_fm)
2684 2 : CALL cp_fm_struct_release(fm_struct)
2685 : END IF
2686 :
2687 : !Giving some PDOS info
2688 2 : output_unit = cp_logger_get_default_io_unit()
2689 2 : IF (output_unit > 0) THEN
2690 : WRITE (UNIT=output_unit, FMT="(/,T5,A,/,T5,A,/,T5,A)") &
2691 1 : "Computing the PDOS of linear-response orbitals for spectral features analysis", &
2692 1 : "Note: using standard PDOS routines => ignore mentions of KS states and MO ", &
2693 2 : " occupation numbers. Eigenvalues in *.pdos files are excitations energies."
2694 : END IF
2695 :
2696 : !Check on NLUMO
2697 2 : CALL section_vals_val_get(xas_tdp_section, "PRINT%PDOS%NLUMO", i_val=nlumo)
2698 2 : IF (nlumo /= 0) THEN
2699 0 : CPWARN("NLUMO is irrelevant for XAS_TDP PDOS. It was overwritten to 0.")
2700 : END IF
2701 2 : CALL section_vals_val_set(xas_tdp_section, "PRINT%PDOS%NLUMO", i_val=0)
2702 : END IF
2703 :
2704 : !CUBES related stuff
2705 4 : IF (do_cubes) THEN
2706 :
2707 2 : print_key => section_vals_get_subs_vals(xas_tdp_section, "PRINT%CUBES")
2708 :
2709 2 : CALL section_vals_val_get(print_key, "CUBES_LU_BOUNDS", i_vals=bounds)
2710 2 : ncubes = bounds(2) - bounds(1) + 1
2711 2 : IF (ncubes > 0) THEN
2712 0 : ALLOCATE (state_list(ncubes))
2713 0 : DO ic = 1, ncubes
2714 0 : state_list(ic) = bounds(1) + ic - 1
2715 : END DO
2716 : END IF
2717 :
2718 2 : IF (.NOT. ASSOCIATED(state_list)) THEN
2719 2 : CALL section_vals_val_get(print_key, "CUBES_LIST", n_rep_val=n_rep)
2720 :
2721 2 : ncubes = 0
2722 4 : DO irep = 1, n_rep
2723 2 : NULLIFY (list)
2724 2 : CALL section_vals_val_get(print_key, "CUBES_LIST", i_rep_val=irep, i_vals=list)
2725 4 : IF (ASSOCIATED(list)) THEN
2726 2 : CALL reallocate(state_list, 1, ncubes + SIZE(list))
2727 4 : DO ic = 1, SIZE(list)
2728 4 : state_list(ncubes + ic) = list(ic)
2729 : END DO
2730 2 : ncubes = ncubes + SIZE(list)
2731 : END IF
2732 : END DO
2733 : END IF
2734 :
2735 2 : IF (.NOT. ASSOCIATED(state_list)) THEN
2736 0 : ncubes = 1
2737 0 : ALLOCATE (state_list(1))
2738 0 : state_list(1) = 1
2739 : END IF
2740 :
2741 2 : CALL section_vals_val_get(print_key, "APPEND", l_val=append_cube)
2742 2 : pos = "REWIND"
2743 2 : IF (append_cube) pos = "APPEND"
2744 :
2745 6 : ALLOCATE (centers(6, ncubes))
2746 18 : centers = 0.0_dp
2747 :
2748 : END IF
2749 :
2750 : !Loop over MOs and spin, one PDOS/CUBE for each
2751 8 : DO ido_mo = 1, ndo_mo
2752 12 : DO ispin = 1, nspins
2753 :
2754 : !need to create a mo set for the LR-orbitals
2755 4 : ALLOCATE (mo_set)
2756 : CALL allocate_mo_set(mo_set, nao=nao, nmo=nmo, nelectron=nmo, n_el_f=REAL(nmo, dp), &
2757 4 : maxocc=1.0_dp, flexible_electron_count=0.0_dp)
2758 4 : CALL init_mo_set(mo_set, fm_ref=mo_coeff, name="PDOS XAS_TDP MOs")
2759 156 : mo_set%eigenvalues(:) = lr_evals(:)
2760 :
2761 : !get the actual coeff => most common case: closed-shell K-edge, can directly take lr_coeffs
2762 4 : IF (nspins == 1 .AND. ndo_mo == 1) THEN
2763 4 : CALL cp_fm_to_fm(lr_coeffs, mo_set%mo_coeff)
2764 : ELSE
2765 0 : DO imo = 1, nmo
2766 : CALL cp_fm_to_fm_submat(msource=lr_coeffs, mtarget=mo_set%mo_coeff, &
2767 : nrow=nao, ncol=1, s_firstrow=1, &
2768 : s_firstcol=(imo - 1)*ndo_so + (ispin - 1)*ndo_mo + ido_mo, &
2769 0 : t_firstrow=1, t_firstcol=imo)
2770 : END DO
2771 : END IF
2772 :
2773 : !naming the output
2774 4 : domon = domo
2775 4 : IF (donor_state%state_type == xas_2p_type) domon = TRIM(domo)//TRIM(ADJUSTL(cp_to_string(ido_mo)))
2776 : xas_mittle = 'xasat'//TRIM(ADJUSTL(cp_to_string(donor_state%at_index)))//'_'// &
2777 4 : TRIM(domon)//'_'//TRIM(excite)
2778 :
2779 4 : IF (do_pdos) THEN
2780 : CALL calculate_projected_dos(mo_set, atomic_kind_set, qs_kind_set, particle_set, &
2781 : qs_env, xas_tdp_section, ispin, xas_mittle, &
2782 2 : external_matrix_shalf=xas_tdp_env%matrix_shalf)
2783 : END IF
2784 :
2785 4 : IF (do_cubes) THEN
2786 : CALL qs_print_cubes(qs_env, mo_set%mo_coeff, ncubes, state_list, centers, &
2787 : print_key=print_key, root=xas_mittle, ispin=ispin, &
2788 2 : file_position=pos)
2789 : END IF
2790 :
2791 : !clean-up
2792 4 : CALL deallocate_mo_set(mo_set)
2793 8 : DEALLOCATE (mo_set)
2794 :
2795 : END DO
2796 : END DO
2797 :
2798 : !clean-up
2799 4 : CALL cp_fm_release(mo_coeff)
2800 4 : CALL cp_fm_struct_release(mo_struct)
2801 4 : IF (do_cubes) DEALLOCATE (centers, state_list)
2802 :
2803 4 : CALL timestop(handle)
2804 :
2805 78 : END SUBROUTINE xas_tdp_post
2806 :
2807 : ! **************************************************************************************************
2808 : !> \brief Computed the LUMOs for the OT eigensolver guesses
2809 : !> \param xas_tdp_env ...
2810 : !> \param xas_tdp_control ...
2811 : !> \param qs_env ...
2812 : !> \note Uses stendard diagonalization. Do not use the stendard make_lumo subroutine as it uses
2813 : !> the OT eigensolver and there is no guarantee that it will converge fast
2814 : ! **************************************************************************************************
2815 20 : SUBROUTINE make_lumo_guess(xas_tdp_env, xas_tdp_control, qs_env)
2816 :
2817 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2818 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2819 : TYPE(qs_environment_type), POINTER :: qs_env
2820 :
2821 : CHARACTER(len=*), PARAMETER :: routineN = 'make_lumo_guess'
2822 :
2823 : INTEGER :: handle, ispin, nao, nelec_spin(2), &
2824 : nlumo(2), nocc(2), nspins
2825 : LOGICAL :: do_os
2826 20 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: evals
2827 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2828 : TYPE(cp_fm_struct_type), POINTER :: fm_struct, lumo_struct
2829 : TYPE(cp_fm_type) :: amatrix, bmatrix, evecs, work_fm
2830 20 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks, matrix_s
2831 : TYPE(mp_para_env_type), POINTER :: para_env
2832 :
2833 20 : NULLIFY (matrix_ks, matrix_s, para_env, blacs_env)
2834 20 : NULLIFY (lumo_struct, fm_struct)
2835 :
2836 20 : CALL timeset(routineN, handle)
2837 :
2838 20 : do_os = xas_tdp_control%do_uks .OR. xas_tdp_control%do_roks
2839 2 : nspins = 1; IF (do_os) nspins = 2
2840 62 : ALLOCATE (xas_tdp_env%lumo_evecs(nspins))
2841 62 : ALLOCATE (xas_tdp_env%lumo_evals(nspins))
2842 : CALL get_qs_env(qs_env, matrix_ks=matrix_ks, matrix_s=matrix_s, nelectron_spin=nelec_spin, &
2843 20 : para_env=para_env, blacs_env=blacs_env)
2844 20 : CALL dbcsr_get_info(matrix_s(1)%matrix, nfullrows_total=nao)
2845 :
2846 20 : IF (do_os) THEN
2847 6 : nlumo = nao - nelec_spin
2848 2 : nocc = nelec_spin
2849 : ELSE
2850 54 : nlumo = nao - nelec_spin(1)/2
2851 54 : nocc = nelec_spin(1)/2
2852 : END IF
2853 :
2854 62 : ALLOCATE (xas_tdp_env%ot_prec(nspins))
2855 :
2856 42 : DO ispin = 1, nspins
2857 :
2858 : !Going through fm to diagonalize
2859 : CALL cp_fm_struct_create(fm_struct, para_env=para_env, context=blacs_env, &
2860 22 : nrow_global=nao, ncol_global=nao)
2861 22 : CALL cp_fm_create(amatrix, fm_struct)
2862 22 : CALL cp_fm_create(bmatrix, fm_struct)
2863 22 : CALL cp_fm_create(evecs, fm_struct)
2864 22 : CALL cp_fm_create(work_fm, fm_struct)
2865 66 : ALLOCATE (evals(nao))
2866 66 : ALLOCATE (xas_tdp_env%lumo_evals(ispin)%array(nlumo(ispin)))
2867 :
2868 22 : CALL copy_dbcsr_to_fm(matrix_ks(ispin)%matrix, amatrix)
2869 22 : CALL copy_dbcsr_to_fm(matrix_s(1)%matrix, bmatrix)
2870 :
2871 : !The actual diagonalization through Cholesky decomposition
2872 22 : CALL cp_fm_geeig(amatrix, bmatrix, evecs, evals, work_fm)
2873 :
2874 : !Storing results
2875 : CALL cp_fm_struct_create(lumo_struct, para_env=para_env, context=blacs_env, &
2876 22 : nrow_global=nao, ncol_global=nlumo(ispin))
2877 22 : CALL cp_fm_create(xas_tdp_env%lumo_evecs(ispin), lumo_struct)
2878 :
2879 : CALL cp_fm_to_fm_submat(evecs, xas_tdp_env%lumo_evecs(ispin), nrow=nao, &
2880 : ncol=nlumo(ispin), s_firstrow=1, s_firstcol=nocc(ispin) + 1, &
2881 22 : t_firstrow=1, t_firstcol=1)
2882 :
2883 1098 : xas_tdp_env%lumo_evals(ispin)%array(1:nlumo(ispin)) = evals(nocc(ispin) + 1:nao)
2884 :
2885 22 : CALL build_ot_spin_prec(evecs, evals, ispin, xas_tdp_env, xas_tdp_control, qs_env)
2886 :
2887 : !clean-up
2888 22 : CALL cp_fm_release(amatrix)
2889 22 : CALL cp_fm_release(bmatrix)
2890 22 : CALL cp_fm_release(evecs)
2891 22 : CALL cp_fm_release(work_fm)
2892 22 : CALL cp_fm_struct_release(fm_struct)
2893 22 : CALL cp_fm_struct_release(lumo_struct)
2894 64 : DEALLOCATE (evals)
2895 : END DO
2896 :
2897 20 : CALL timestop(handle)
2898 :
2899 60 : END SUBROUTINE make_lumo_guess
2900 :
2901 : ! **************************************************************************************************
2902 : !> \brief Builds a preconditioner for the OT eigensolver, based on some heurstics that prioritize
2903 : !> LUMOs with lower eigenvalues
2904 : !> \param evecs all the ground state eigenvectors
2905 : !> \param evals all the ground state eigenvalues
2906 : !> \param ispin ...
2907 : !> \param xas_tdp_env ...
2908 : !> \param xas_tdp_control ...
2909 : !> \param qs_env ...
2910 : !> \note assumes that the preconditioner matrix array is allocated
2911 : ! **************************************************************************************************
2912 22 : SUBROUTINE build_ot_spin_prec(evecs, evals, ispin, xas_tdp_env, xas_tdp_control, qs_env)
2913 :
2914 : TYPE(cp_fm_type), INTENT(IN) :: evecs
2915 : REAL(dp), DIMENSION(:) :: evals
2916 : INTEGER :: ispin
2917 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2918 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2919 : TYPE(qs_environment_type), POINTER :: qs_env
2920 :
2921 : CHARACTER(len=*), PARAMETER :: routineN = 'build_ot_spin_prec'
2922 :
2923 : INTEGER :: handle, nao, nelec_spin(2), nguess, &
2924 : nocc, nspins
2925 : LOGICAL :: do_os
2926 : REAL(dp) :: shift
2927 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: scaling
2928 : TYPE(cp_fm_struct_type), POINTER :: fm_struct
2929 : TYPE(cp_fm_type) :: fm_prec, work_fm
2930 22 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_s
2931 : TYPE(mp_para_env_type), POINTER :: para_env
2932 :
2933 22 : NULLIFY (fm_struct, para_env, matrix_s)
2934 :
2935 22 : CALL timeset(routineN, handle)
2936 :
2937 22 : do_os = xas_tdp_control%do_uks .OR. xas_tdp_control%do_roks
2938 22 : CALL get_qs_env(qs_env, para_env=para_env, nelectron_spin=nelec_spin, matrix_s=matrix_s)
2939 22 : CALL cp_fm_get_info(evecs, nrow_global=nao, matrix_struct=fm_struct)
2940 22 : CALL cp_fm_create(fm_prec, fm_struct)
2941 66 : ALLOCATE (scaling(nao))
2942 22 : nocc = nelec_spin(1)/2
2943 22 : nspins = 1
2944 22 : IF (do_os) THEN
2945 4 : nocc = nelec_spin(ispin)
2946 4 : nspins = 2
2947 : END IF
2948 :
2949 : !rough estimate of the number of required evals
2950 22 : nguess = nao - nocc
2951 22 : IF (xas_tdp_control%n_excited > 0 .AND. xas_tdp_control%n_excited < nguess) THEN
2952 4 : nguess = xas_tdp_control%n_excited/nspins
2953 18 : ELSE IF (xas_tdp_control%e_range > 0.0_dp) THEN
2954 514 : nguess = COUNT(evals(nocc + 1:nao) - evals(nocc + 1) <= xas_tdp_control%e_range)
2955 : END IF
2956 :
2957 : !Give max weight to the first LUMOs
2958 540 : scaling(nocc + 1:nocc + nguess) = 100.0_dp
2959 : !Then gradually decrease weight
2960 22 : shift = evals(nocc + 1) - 0.01_dp
2961 602 : scaling(nocc + nguess:nao) = 1.0_dp/(evals(nocc + nguess:nao) - shift)
2962 : !HOMOs do not matter, but need well behaved matrix
2963 616 : scaling(1:nocc) = 1.0_dp
2964 :
2965 : !Building the precond as an fm
2966 22 : CALL cp_fm_create(work_fm, fm_struct)
2967 :
2968 22 : CALL cp_fm_copy_general(evecs, work_fm, para_env)
2969 22 : CALL cp_fm_column_scale(work_fm, scaling)
2970 :
2971 22 : CALL parallel_gemm('N', 'T', nao, nao, nao, 1.0_dp, work_fm, evecs, 0.0_dp, fm_prec)
2972 :
2973 : !Copy into dbcsr format
2974 22 : ALLOCATE (xas_tdp_env%ot_prec(ispin)%matrix)
2975 22 : CALL dbcsr_create(xas_tdp_env%ot_prec(ispin)%matrix, template=matrix_s(1)%matrix, name="OT_PREC")
2976 22 : CALL copy_fm_to_dbcsr(fm_prec, xas_tdp_env%ot_prec(ispin)%matrix)
2977 22 : CALL dbcsr_filter(xas_tdp_env%ot_prec(ispin)%matrix, xas_tdp_control%eps_filter)
2978 :
2979 22 : CALL cp_fm_release(work_fm)
2980 22 : CALL cp_fm_release(fm_prec)
2981 :
2982 22 : CALL timestop(handle)
2983 :
2984 88 : END SUBROUTINE build_ot_spin_prec
2985 :
2986 : ! **************************************************************************************************
2987 : !> \brief Prints GW2X corrected ionization potentials to main output file, including SOC splitting
2988 : !> \param donor_state ...
2989 : !> \param xas_tdp_env ...
2990 : !> \param xas_tdp_control ...
2991 : !> \param qs_env ...
2992 : ! **************************************************************************************************
2993 30 : SUBROUTINE print_xps(donor_state, xas_tdp_env, xas_tdp_control, qs_env)
2994 :
2995 : TYPE(donor_state_type), POINTER :: donor_state
2996 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2997 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2998 : TYPE(qs_environment_type), POINTER :: qs_env
2999 :
3000 : INTEGER :: ido_mo, ispin, nspins, output_unit
3001 30 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: IPs, soc_shifts
3002 :
3003 30 : output_unit = cp_logger_get_default_io_unit()
3004 :
3005 30 : nspins = 1; IF (xas_tdp_control%do_uks .OR. xas_tdp_control%do_roks) nspins = 2
3006 :
3007 120 : ALLOCATE (IPs(SIZE(donor_state%gw2x_evals, 1), SIZE(donor_state%gw2x_evals, 2)))
3008 106 : IPs(:, :) = donor_state%gw2x_evals(:, :)
3009 :
3010 : !IPs in PBCs cannot be trusted because of a lack of a potential reference
3011 30 : IF (.NOT. xas_tdp_control%is_periodic) THEN
3012 :
3013 : !Apply SOC splitting
3014 26 : IF (donor_state%ndo_mo > 1) THEN
3015 : CALL get_soc_splitting(soc_shifts, donor_state, xas_tdp_env, xas_tdp_control, qs_env)
3016 20 : IPs(:, :) = IPs(:, :) + soc_shifts
3017 :
3018 4 : IF (output_unit > 0) THEN
3019 : WRITE (output_unit, FMT="(/,T5,A,F23.6)") &
3020 2 : "Ionization potentials for XPS (GW2X + SOC): ", -IPs(1, 1)*evolt
3021 :
3022 4 : DO ispin = 1, nspins
3023 10 : DO ido_mo = 1, donor_state%ndo_mo
3024 :
3025 6 : IF (ispin == 1 .AND. ido_mo == 1) CYCLE
3026 :
3027 : WRITE (output_unit, FMT="(T5,A,F23.6)") &
3028 8 : " ", -IPs(ido_mo, ispin)*evolt
3029 :
3030 : END DO
3031 : END DO
3032 : END IF
3033 :
3034 : ELSE
3035 :
3036 : ! No SOC, only 1 donor MO per spin
3037 22 : IF (output_unit > 0) THEN
3038 : WRITE (output_unit, FMT="(/,T5,A,F29.6)") &
3039 11 : "Ionization potentials for XPS (GW2X): ", -IPs(1, 1)*evolt
3040 :
3041 11 : IF (nspins == 2) THEN
3042 : WRITE (output_unit, FMT="(T5,A,F29.6)") &
3043 2 : " ", -IPs(1, 2)*evolt
3044 : END IF
3045 : END IF
3046 :
3047 : END IF
3048 : END IF
3049 :
3050 30 : END SUBROUTINE print_xps
3051 :
3052 : ! **************************************************************************************************
3053 : !> \brief Prints the excitation energies and the oscillator strengths for a given donor_state in a file
3054 : !> \param donor_state the donor_state to print
3055 : !> \param xas_tdp_env ...
3056 : !> \param xas_tdp_control ...
3057 : !> \param xas_tdp_section ...
3058 : ! **************************************************************************************************
3059 72 : SUBROUTINE print_xas_tdp_to_file(donor_state, xas_tdp_env, xas_tdp_control, xas_tdp_section)
3060 :
3061 : TYPE(donor_state_type), POINTER :: donor_state
3062 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
3063 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
3064 : TYPE(section_vals_type), POINTER :: xas_tdp_section
3065 :
3066 : INTEGER :: i, output_unit, xas_tdp_unit
3067 : TYPE(cp_logger_type), POINTER :: logger
3068 :
3069 72 : NULLIFY (logger)
3070 72 : logger => cp_get_default_logger()
3071 :
3072 : xas_tdp_unit = cp_print_key_unit_nr(logger, xas_tdp_section, "PRINT%SPECTRUM", &
3073 : extension=".spectrum", file_position="APPEND", &
3074 72 : file_action="WRITE", file_form="FORMATTED")
3075 :
3076 72 : output_unit = cp_logger_get_default_io_unit()
3077 :
3078 72 : IF (output_unit > 0) THEN
3079 : WRITE (output_unit, FMT="(/,T5,A,/)") &
3080 36 : "Calculations done: "
3081 : END IF
3082 :
3083 72 : IF (xas_tdp_control%do_spin_cons) THEN
3084 12 : IF (xas_tdp_unit > 0) THEN
3085 :
3086 : ! Printing the general donor state information
3087 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3088 6 : "==================================================================================", &
3089 6 : "XAS TDP open-shell spin-conserving (no SOC) excitations for DONOR STATE: ", &
3090 6 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3091 6 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3092 6 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3093 12 : "=================================================================================="
3094 :
3095 : ! Simply dump the excitation energies/ oscillator strength as they come
3096 :
3097 6 : IF (xas_tdp_control%do_quad) THEN
3098 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3099 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3100 0 : DO i = 1, SIZE(donor_state%sc_evals)
3101 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3102 0 : i, donor_state%sc_evals(i)*evolt, donor_state%osc_str(i, 4), &
3103 0 : donor_state%quad_osc_str(i)
3104 : END DO
3105 6 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3106 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3107 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3108 0 : DO i = 1, SIZE(donor_state%sc_evals)
3109 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3110 0 : i, donor_state%sc_evals(i)*evolt, donor_state%osc_str(i, 4), &
3111 0 : donor_state%osc_str(i, 1), donor_state%osc_str(i, 2), donor_state%osc_str(i, 3)
3112 : END DO
3113 6 : ELSE IF (xas_tdp_control%spin_dip) THEN
3114 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3115 0 : " Index Excitation energy (eV) fosc dipole (a.u.) alpha-comp beta-comp"
3116 0 : DO i = 1, SIZE(donor_state%sc_evals)
3117 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6)") &
3118 0 : i, donor_state%sc_evals(i)*evolt, donor_state%osc_str(i, 4), &
3119 0 : donor_state%alpha_osc(i, 4), donor_state%beta_osc(i, 4)
3120 : END DO
3121 : ELSE
3122 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3123 6 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3124 134 : DO i = 1, SIZE(donor_state%sc_evals)
3125 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3126 134 : i, donor_state%sc_evals(i)*evolt, donor_state%osc_str(i, 4)
3127 : END DO
3128 : END IF
3129 :
3130 6 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3131 : END IF !xas_tdp_unit > 0
3132 :
3133 12 : IF (output_unit > 0) THEN
3134 : WRITE (output_unit, FMT="(T5,A,F17.6)") &
3135 6 : "First spin-conserving XAS excitation energy (eV): ", donor_state%sc_evals(1)*evolt
3136 : END IF
3137 :
3138 : END IF ! do_spin_cons
3139 :
3140 72 : IF (xas_tdp_control%do_spin_flip) THEN
3141 2 : IF (xas_tdp_unit > 0) THEN
3142 :
3143 : ! Printing the general donor state information
3144 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3145 1 : "==================================================================================", &
3146 1 : "XAS TDP open-shell spin-flip (no SOC) excitations for DONOR STATE: ", &
3147 1 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3148 1 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3149 1 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3150 2 : "=================================================================================="
3151 :
3152 : ! Simply dump the excitation energies/ oscillator strength as they come
3153 :
3154 1 : IF (xas_tdp_control%do_quad) THEN
3155 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3156 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3157 0 : DO i = 1, SIZE(donor_state%sf_evals)
3158 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3159 0 : i, donor_state%sf_evals(i)*evolt, 0.0_dp, 0.0_dp !spin-forbidden !
3160 : END DO
3161 1 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3162 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3163 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3164 0 : DO i = 1, SIZE(donor_state%sf_evals)
3165 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3166 0 : i, donor_state%sf_evals(i)*evolt, 0.0_dp, 0.0_dp, 0.0_dp, 0.0_dp
3167 : END DO
3168 1 : ELSE IF (xas_tdp_control%spin_dip) THEN
3169 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3170 0 : " Index Excitation energy (eV) fosc dipole (a.u.) alpha-comp beta-comp"
3171 0 : DO i = 1, SIZE(donor_state%sf_evals)
3172 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6)") &
3173 0 : i, donor_state%sf_evals(i)*evolt, 0.0_dp, 0.0_dp, 0.0_dp
3174 : END DO
3175 : ELSE
3176 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3177 1 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3178 13 : DO i = 1, SIZE(donor_state%sf_evals)
3179 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3180 13 : i, donor_state%sf_evals(i)*evolt, 0.0_dp
3181 : END DO
3182 : END IF
3183 :
3184 1 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3185 : END IF !xas_tdp_unit
3186 :
3187 2 : IF (output_unit > 0) THEN
3188 : WRITE (output_unit, FMT="(T5,A,F23.6)") &
3189 1 : "First spin-flip XAS excitation energy (eV): ", donor_state%sf_evals(1)*evolt
3190 : END IF
3191 : END IF ! do_spin_flip
3192 :
3193 72 : IF (xas_tdp_control%do_singlet) THEN
3194 60 : IF (xas_tdp_unit > 0) THEN
3195 :
3196 : ! Printing the general donor state information
3197 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3198 30 : "==================================================================================", &
3199 30 : "XAS TDP singlet excitations (no SOC) for DONOR STATE: ", &
3200 30 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3201 30 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3202 30 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3203 60 : "=================================================================================="
3204 :
3205 : ! Simply dump the excitation energies/ oscillator strength as they come
3206 :
3207 30 : IF (xas_tdp_control%do_quad) THEN
3208 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3209 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3210 0 : DO i = 1, SIZE(donor_state%sg_evals)
3211 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3212 0 : i, donor_state%sg_evals(i)*evolt, donor_state%osc_str(i, 4), &
3213 0 : donor_state%quad_osc_str(i)
3214 : END DO
3215 30 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3216 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3217 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3218 0 : DO i = 1, SIZE(donor_state%sg_evals)
3219 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3220 0 : i, donor_state%sg_evals(i)*evolt, donor_state%osc_str(i, 4), &
3221 0 : donor_state%osc_str(i, 1), donor_state%osc_str(i, 2), donor_state%osc_str(i, 3)
3222 : END DO
3223 : ELSE
3224 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3225 30 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3226 438 : DO i = 1, SIZE(donor_state%sg_evals)
3227 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3228 438 : i, donor_state%sg_evals(i)*evolt, donor_state%osc_str(i, 4)
3229 : END DO
3230 : END IF
3231 :
3232 30 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3233 : END IF !xas_tdp_unit
3234 :
3235 60 : IF (output_unit > 0) THEN
3236 : WRITE (output_unit, FMT="(T5,A,F25.6)") &
3237 30 : "First singlet XAS excitation energy (eV): ", donor_state%sg_evals(1)*evolt
3238 : END IF
3239 : END IF ! do_singlet
3240 :
3241 72 : IF (xas_tdp_control%do_triplet) THEN
3242 2 : IF (xas_tdp_unit > 0) THEN
3243 :
3244 : ! Printing the general donor state information
3245 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3246 1 : "==================================================================================", &
3247 1 : "XAS TDP triplet excitations (no SOC) for DONOR STATE: ", &
3248 1 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3249 1 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3250 1 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3251 2 : "=================================================================================="
3252 :
3253 : ! Simply dump the excitation energies/ oscillator strength as they come
3254 :
3255 1 : IF (xas_tdp_control%do_quad) THEN
3256 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3257 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3258 0 : DO i = 1, SIZE(donor_state%tp_evals)
3259 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3260 0 : i, donor_state%tp_evals(i)*evolt, 0.0_dp, 0.0_dp !spin-forbidden !
3261 : END DO
3262 1 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3263 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3264 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3265 0 : DO i = 1, SIZE(donor_state%tp_evals)
3266 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3267 0 : i, donor_state%tp_evals(i)*evolt, 0.0_dp, 0.0_dp, 0.0_dp, 0.0_dp
3268 : END DO
3269 1 : ELSE IF (xas_tdp_control%spin_dip) THEN
3270 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3271 0 : " Index Excitation energy (eV) fosc dipole (a.u.) alpha-comp beta-comp"
3272 0 : DO i = 1, SIZE(donor_state%tp_evals)
3273 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6)") &
3274 0 : i, donor_state%tp_evals(i)*evolt, 0.0_dp, 0.0_dp, 0.0_dp
3275 : END DO
3276 : ELSE
3277 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3278 1 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3279 13 : DO i = 1, SIZE(donor_state%tp_evals)
3280 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3281 13 : i, donor_state%tp_evals(i)*evolt, 0.0_dp
3282 : END DO
3283 : END IF
3284 :
3285 1 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3286 : END IF !xas_tdp_unit
3287 :
3288 2 : IF (output_unit > 0) THEN
3289 : WRITE (output_unit, FMT="(T5,A,F25.6)") &
3290 1 : "First triplet XAS excitation energy (eV): ", donor_state%tp_evals(1)*evolt
3291 : END IF
3292 : END IF ! do_triplet
3293 :
3294 72 : IF (xas_tdp_control%do_soc .AND. donor_state%state_type == xas_2p_type) THEN
3295 4 : IF (xas_tdp_unit > 0) THEN
3296 :
3297 : ! Printing the general donor state information
3298 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3299 2 : "==================================================================================", &
3300 2 : "XAS TDP excitations after spin-orbit coupling for DONOR STATE: ", &
3301 2 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3302 2 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3303 2 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3304 4 : "=================================================================================="
3305 :
3306 : ! Simply dump the excitation energies/ oscillator strength as they come
3307 2 : IF (xas_tdp_control%do_quad) THEN
3308 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3309 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3310 0 : DO i = 1, SIZE(donor_state%soc_evals)
3311 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3312 0 : i, donor_state%soc_evals(i)*evolt, donor_state%soc_osc_str(i, 4), &
3313 0 : donor_state%soc_quad_osc_str(i)
3314 : END DO
3315 2 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3316 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3317 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3318 0 : DO i = 1, SIZE(donor_state%soc_evals)
3319 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3320 0 : i, donor_state%soc_evals(i)*evolt, donor_state%soc_osc_str(i, 4), &
3321 0 : donor_state%soc_osc_str(i, 1), donor_state%soc_osc_str(i, 2), donor_state%soc_osc_str(i, 3)
3322 : END DO
3323 : ELSE
3324 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3325 2 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3326 74 : DO i = 1, SIZE(donor_state%soc_evals)
3327 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3328 74 : i, donor_state%soc_evals(i)*evolt, donor_state%soc_osc_str(i, 4)
3329 : END DO
3330 : END IF
3331 :
3332 2 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3333 : END IF !xas_tdp_unit
3334 :
3335 4 : IF (output_unit > 0) THEN
3336 : WRITE (output_unit, FMT="(T5,A,F29.6)") &
3337 2 : "First SOC XAS excitation energy (eV): ", donor_state%soc_evals(1)*evolt
3338 : END IF
3339 : END IF !do_soc
3340 :
3341 72 : CALL cp_print_key_finished_output(xas_tdp_unit, logger, xas_tdp_section, "PRINT%SPECTRUM")
3342 :
3343 72 : END SUBROUTINE print_xas_tdp_to_file
3344 :
3345 : ! **************************************************************************************************
3346 : !> \brief Prints the donor_state and excitation_type info into a RESTART file for cheap PDOS and/or
3347 : !> CUBE printing without expensive computation
3348 : !> \param ex_type singlet, triplet, etc.
3349 : !> \param donor_state ...
3350 : !> \param xas_tdp_section ...
3351 : !> \param qs_env ...
3352 : ! **************************************************************************************************
3353 80 : SUBROUTINE write_donor_state_restart(ex_type, donor_state, xas_tdp_section, qs_env)
3354 :
3355 : INTEGER, INTENT(IN) :: ex_type
3356 : TYPE(donor_state_type), POINTER :: donor_state
3357 : TYPE(section_vals_type), POINTER :: xas_tdp_section
3358 : TYPE(qs_environment_type), POINTER :: qs_env
3359 :
3360 : CHARACTER(len=*), PARAMETER :: routineN = 'write_donor_state_restart'
3361 :
3362 : CHARACTER(len=default_path_length) :: filename
3363 : CHARACTER(len=default_string_length) :: domo, excite, my_middle
3364 : INTEGER :: ex_atom, handle, ispin, nao, ndo_mo, &
3365 : nex, nspins, output_unit, rst_unit, &
3366 : state_type
3367 76 : INTEGER, DIMENSION(:, :), POINTER :: mo_indices
3368 : LOGICAL :: do_print
3369 76 : REAL(dp), DIMENSION(:), POINTER :: lr_evals
3370 : TYPE(cp_fm_type), POINTER :: lr_coeffs
3371 : TYPE(cp_logger_type), POINTER :: logger
3372 76 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
3373 : TYPE(section_vals_type), POINTER :: print_key
3374 :
3375 76 : NULLIFY (logger, lr_coeffs, lr_evals, print_key, mos)
3376 :
3377 : !Initialization
3378 152 : logger => cp_get_default_logger()
3379 76 : do_print = .FALSE.
3380 76 : IF (BTEST(cp_print_key_should_output(logger%iter_info, xas_tdp_section, &
3381 : "PRINT%RESTART", used_print_key=print_key), cp_p_file)) do_print = .TRUE.
3382 :
3383 74 : IF (.NOT. do_print) RETURN
3384 :
3385 2 : CALL timeset(routineN, handle)
3386 :
3387 2 : output_unit = cp_logger_get_default_io_unit()
3388 :
3389 : !Get general info
3390 2 : SELECT CASE (ex_type)
3391 : CASE (tddfpt_spin_cons)
3392 0 : lr_evals => donor_state%sc_evals
3393 0 : lr_coeffs => donor_state%sc_coeffs
3394 0 : excite = "spincons"
3395 0 : nspins = 2
3396 : CASE (tddfpt_spin_flip)
3397 0 : lr_evals => donor_state%sf_evals
3398 0 : lr_coeffs => donor_state%sf_coeffs
3399 0 : excite = "spinflip"
3400 0 : nspins = 2
3401 : CASE (tddfpt_singlet)
3402 2 : lr_evals => donor_state%sg_evals
3403 2 : lr_coeffs => donor_state%sg_coeffs
3404 2 : excite = "singlet"
3405 2 : nspins = 1
3406 : CASE (tddfpt_triplet)
3407 0 : lr_evals => donor_state%tp_evals
3408 0 : lr_coeffs => donor_state%tp_coeffs
3409 0 : excite = "triplet"
3410 2 : nspins = 1
3411 : END SELECT
3412 :
3413 4 : SELECT CASE (donor_state%state_type)
3414 : CASE (xas_1s_type)
3415 2 : domo = "1s"
3416 : CASE (xas_2s_type)
3417 0 : domo = "2s"
3418 : CASE (xas_2p_type)
3419 2 : domo = "2p"
3420 : END SELECT
3421 :
3422 2 : ndo_mo = donor_state%ndo_mo
3423 2 : nex = SIZE(lr_evals)
3424 2 : CALL cp_fm_get_info(lr_coeffs, nrow_global=nao)
3425 2 : state_type = donor_state%state_type
3426 2 : ex_atom = donor_state%at_index
3427 2 : mo_indices => donor_state%mo_indices
3428 :
3429 : !Opening restart file
3430 2 : rst_unit = -1
3431 2 : my_middle = 'xasat'//TRIM(ADJUSTL(cp_to_string(ex_atom)))//'_'//TRIM(domo)//'_'//TRIM(excite)
3432 : rst_unit = cp_print_key_unit_nr(logger, xas_tdp_section, "PRINT%RESTART", extension=".rst", &
3433 : file_status="REPLACE", file_action="WRITE", &
3434 2 : file_form="UNFORMATTED", middle_name=TRIM(my_middle))
3435 :
3436 : filename = cp_print_key_generate_filename(logger, print_key, middle_name=TRIM(my_middle), &
3437 2 : extension=".rst", my_local=.FALSE.)
3438 :
3439 2 : IF (output_unit > 0) THEN
3440 : WRITE (UNIT=output_unit, FMT="(/,T5,A,/T5,A,A,A)") &
3441 1 : "Linear-response orbitals and excitation energies are written in: ", &
3442 2 : '"', TRIM(filename), '"'
3443 : END IF
3444 :
3445 : !Writing
3446 2 : IF (rst_unit > 0) THEN
3447 1 : WRITE (rst_unit) ex_atom, state_type, ndo_mo, ex_type
3448 1 : WRITE (rst_unit) nao, nex, nspins
3449 1 : WRITE (rst_unit) mo_indices(:, :)
3450 1 : WRITE (rst_unit) lr_evals(:)
3451 : END IF
3452 2 : CALL cp_fm_write_unformatted(lr_coeffs, rst_unit)
3453 :
3454 : !The MOs as well (because the may have been localized)
3455 2 : CALL get_qs_env(qs_env, mos=mos)
3456 4 : DO ispin = 1, nspins
3457 4 : CALL cp_fm_write_unformatted(mos(ispin)%mo_coeff, rst_unit)
3458 : END DO
3459 :
3460 : !closing
3461 2 : CALL cp_print_key_finished_output(rst_unit, logger, xas_tdp_section, "PRINT%RESTART")
3462 :
3463 2 : CALL timestop(handle)
3464 :
3465 76 : END SUBROUTINE write_donor_state_restart
3466 :
3467 : ! **************************************************************************************************
3468 : !> \brief Reads donor_state info from a restart file
3469 : !> \param donor_state the pre-allocated donor_state
3470 : !> \param ex_type the excitations stored in this specific file
3471 : !> \param filename the restart file to read from
3472 : !> \param qs_env ...
3473 : ! **************************************************************************************************
3474 2 : SUBROUTINE read_donor_state_restart(donor_state, ex_type, filename, qs_env)
3475 :
3476 : TYPE(donor_state_type), POINTER :: donor_state
3477 : INTEGER, INTENT(OUT) :: ex_type
3478 : CHARACTER(len=*), INTENT(IN) :: filename
3479 : TYPE(qs_environment_type), POINTER :: qs_env
3480 :
3481 : CHARACTER(len=*), PARAMETER :: routineN = 'read_donor_state_restart'
3482 :
3483 : INTEGER :: handle, ispin, nao, nex, nspins, &
3484 : output_unit, read_params(7), rst_unit
3485 2 : INTEGER, DIMENSION(:, :), POINTER :: mo_indices
3486 : LOGICAL :: file_exists
3487 2 : REAL(dp), DIMENSION(:), POINTER :: lr_evals
3488 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
3489 : TYPE(cp_fm_struct_type), POINTER :: fm_struct
3490 : TYPE(cp_fm_type), POINTER :: lr_coeffs
3491 2 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
3492 : TYPE(mp_comm_type) :: group
3493 : TYPE(mp_para_env_type), POINTER :: para_env
3494 :
3495 2 : NULLIFY (lr_evals, lr_coeffs, para_env, fm_struct, blacs_env, mos)
3496 :
3497 2 : CALL timeset(routineN, handle)
3498 :
3499 2 : output_unit = cp_logger_get_default_io_unit()
3500 2 : CPASSERT(ASSOCIATED(donor_state))
3501 2 : CALL get_qs_env(qs_env, para_env=para_env, blacs_env=blacs_env)
3502 2 : group = para_env
3503 :
3504 2 : file_exists = .FALSE.
3505 2 : rst_unit = -1
3506 :
3507 2 : IF (para_env%is_source()) THEN
3508 :
3509 1 : INQUIRE (FILE=filename, EXIST=file_exists)
3510 1 : IF (.NOT. file_exists) CPABORT("Trying to read non-existing XAS_TDP restart file")
3511 :
3512 : CALL open_file(file_name=TRIM(filename), file_action="READ", file_form="UNFORMATTED", &
3513 1 : file_position="REWIND", file_status="OLD", unit_number=rst_unit)
3514 : END IF
3515 :
3516 2 : IF (output_unit > 0) THEN
3517 : WRITE (UNIT=output_unit, FMT="(/,T5,A,/,T5,A,A,A)") &
3518 1 : "Reading linear-response orbitals and excitation energies from file: ", &
3519 2 : '"', filename, '"'
3520 : END IF
3521 :
3522 : !read general params
3523 2 : IF (rst_unit > 0) THEN
3524 1 : READ (rst_unit) read_params(1:4)
3525 1 : READ (rst_unit) read_params(5:7)
3526 : END IF
3527 2 : CALL group%bcast(read_params)
3528 2 : donor_state%at_index = read_params(1)
3529 2 : donor_state%state_type = read_params(2)
3530 2 : donor_state%ndo_mo = read_params(3)
3531 2 : ex_type = read_params(4)
3532 2 : nao = read_params(5)
3533 2 : nex = read_params(6)
3534 2 : nspins = read_params(7)
3535 :
3536 8 : ALLOCATE (mo_indices(donor_state%ndo_mo, nspins))
3537 2 : IF (rst_unit > 0) THEN
3538 1 : READ (rst_unit) mo_indices(1:donor_state%ndo_mo, 1:nspins)
3539 : END IF
3540 10 : CALL group%bcast(mo_indices)
3541 2 : donor_state%mo_indices => mo_indices
3542 :
3543 : !read evals
3544 6 : ALLOCATE (lr_evals(nex))
3545 2 : IF (rst_unit > 0) READ (rst_unit) lr_evals(1:nex)
3546 78 : CALL group%bcast(lr_evals)
3547 :
3548 : !read evecs
3549 : CALL cp_fm_struct_create(fm_struct, context=blacs_env, para_env=para_env, &
3550 2 : nrow_global=nao, ncol_global=nex*donor_state%ndo_mo*nspins)
3551 2 : ALLOCATE (lr_coeffs)
3552 2 : CALL cp_fm_create(lr_coeffs, fm_struct)
3553 2 : CALL cp_fm_read_unformatted(lr_coeffs, rst_unit)
3554 2 : CALL cp_fm_struct_release(fm_struct)
3555 :
3556 : !read MO coeffs and replace in qs_env
3557 2 : CALL get_qs_env(qs_env, mos=mos)
3558 4 : DO ispin = 1, nspins
3559 4 : CALL cp_fm_read_unformatted(mos(ispin)%mo_coeff, rst_unit)
3560 : END DO
3561 :
3562 : !closing file
3563 2 : IF (para_env%is_source()) THEN
3564 1 : CALL close_file(unit_number=rst_unit)
3565 : END IF
3566 :
3567 : !case study on excitation type
3568 2 : SELECT CASE (ex_type)
3569 : CASE (tddfpt_spin_cons)
3570 0 : donor_state%sc_evals => lr_evals
3571 0 : donor_state%sc_coeffs => lr_coeffs
3572 : CASE (tddfpt_spin_flip)
3573 0 : donor_state%sf_evals => lr_evals
3574 0 : donor_state%sf_coeffs => lr_coeffs
3575 : CASE (tddfpt_singlet)
3576 2 : donor_state%sg_evals => lr_evals
3577 2 : donor_state%sg_coeffs => lr_coeffs
3578 : CASE (tddfpt_triplet)
3579 0 : donor_state%tp_evals => lr_evals
3580 2 : donor_state%tp_coeffs => lr_coeffs
3581 : END SELECT
3582 :
3583 2 : CALL timestop(handle)
3584 :
3585 4 : END SUBROUTINE read_donor_state_restart
3586 :
3587 : ! **************************************************************************************************
3588 : !> \brief Checks whether this is a restart calculation and runs it if so
3589 : !> \param rst_filename the file to read for restart
3590 : !> \param xas_tdp_section ...
3591 : !> \param qs_env ...
3592 : ! **************************************************************************************************
3593 4 : SUBROUTINE restart_calculation(rst_filename, xas_tdp_section, qs_env)
3594 :
3595 : CHARACTER(len=*), INTENT(IN) :: rst_filename
3596 : TYPE(section_vals_type), POINTER :: xas_tdp_section
3597 : TYPE(qs_environment_type), POINTER :: qs_env
3598 :
3599 : INTEGER :: ex_type
3600 : TYPE(donor_state_type), POINTER :: donor_state
3601 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
3602 :
3603 2 : NULLIFY (xas_tdp_env, donor_state)
3604 :
3605 : !create a donor_state that we fill with the information we read
3606 2 : ALLOCATE (donor_state)
3607 2 : CALL donor_state_create(donor_state)
3608 2 : CALL read_donor_state_restart(donor_state, ex_type, rst_filename, qs_env)
3609 :
3610 : !create a dummy xas_tdp_env and compute the post XAS_TDP stuff
3611 2 : CALL xas_tdp_env_create(xas_tdp_env)
3612 2 : CALL xas_tdp_post(ex_type, donor_state, xas_tdp_env, xas_tdp_section, qs_env)
3613 :
3614 : !clean-up
3615 2 : CALL xas_tdp_env_release(xas_tdp_env)
3616 2 : CALL free_ds_memory(donor_state)
3617 2 : DEALLOCATE (donor_state%mo_indices)
3618 2 : DEALLOCATE (donor_state)
3619 :
3620 2 : END SUBROUTINE restart_calculation
3621 :
3622 : END MODULE xas_tdp_methods
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