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 : ! **************************************************************************************************
166 120 : 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 60 : CALL timeset(routineN, handle)
179 :
180 : ! Logger initialization and XAS TDP banner printing
181 60 : NULLIFY (xas_tdp_section)
182 :
183 : ! check if subroutine is called as part of rixs calculation
184 60 : CALL get_qs_env(qs_env, do_rixs=do_rixs)
185 60 : IF (do_rixs) THEN
186 10 : 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 60 : output_unit = cp_logger_get_default_io_unit()
191 :
192 60 : IF (output_unit > 0) THEN
193 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/,T3,A,/,T3,A,/,T3,A,/)") &
194 30 : "!===========================================================================!", &
195 30 : "! XAS TDP !", &
196 30 : "! Starting TDDFPT driven X-rays absorption spectroscopy calculations !", &
197 60 : "!===========================================================================!"
198 : END IF
199 :
200 60 : CALL cite_reference(Bussy2021a)
201 :
202 : ! Check whether this is a restart calculation, i.e. is a restart file is provided
203 60 : CALL section_vals_val_get(xas_tdp_section, "RESTART_FROM_FILE", n_rep_val=n_rep)
204 :
205 60 : 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 58 : IF (PRESENT(rixs_env)) THEN
225 10 : 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 60 : IF (output_unit > 0) THEN
232 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/,T3,A,/,T3,A,/)") &
233 30 : "!===========================================================================!", &
234 30 : "! End of TDDFPT driven X-rays absorption spectroscopy calculations !", &
235 60 : "!===========================================================================!"
236 : END IF
237 :
238 60 : CALL timestop(handle)
239 :
240 60 : 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 58 : 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 58 : INTEGER, ALLOCATABLE, DIMENSION(:) :: batch_atoms, ex_atoms_of_kind
258 58 : INTEGER, DIMENSION(:), POINTER :: atoms_of_kind
259 : LOGICAL :: do_os, do_rixs, end_of_batch, unique
260 : TYPE(admm_type), POINTER :: admm_env
261 58 : TYPE(atomic_kind_type), DIMENSION(:), POINTER :: atomic_kind_set
262 58 : 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 58 : 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 58 : NULLIFY (xas_tdp_env, xas_tdp_control, atomic_kind_set, atoms_of_kind, current_state)
272 58 : NULLIFY (xas_atom_env, dft_control, matrix_ks, admm_env, qs_kind_set, tmp_basis)
273 :
274 : ! Initialization
275 116 : output_unit = cp_logger_get_default_io_unit()
276 :
277 58 : IF (output_unit > 0) THEN
278 : WRITE (UNIT=output_unit, FMT="(/,T3,A)") &
279 29 : "# Create and initialize the XAS_TDP environment"
280 : END IF
281 58 : CALL get_qs_env(qs_env, dft_control=dft_control, do_rixs=do_rixs)
282 58 : IF (PRESENT(rixs_env)) THEN
283 10 : 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 58 : CALL print_info(output_unit, xas_tdp_control, qs_env)
288 :
289 58 : IF (output_unit > 0) THEN
290 29 : 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 58 : 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 58 : CALL find_mo_centers(xas_tdp_env, xas_tdp_control, qs_env)
315 :
316 : ! Assign lowest energy orbitals to excited atoms
317 58 : 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 58 : 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 58 : IF (output_unit > 0) THEN
332 : WRITE (UNIT=output_unit, FMT="(/,T3,A,I4,A,/)") &
333 29 : "# Assign the relevant subset of the ", xas_tdp_control%n_search, &
334 58 : " lowest energy MOs to excited atoms"
335 : END IF
336 58 : 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 58 : 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 58 : .AND. .NOT. xas_tdp_control%check_only) THEN
345 :
346 58 : IF (output_unit > 0 .AND. xas_tdp_control%do_xc) THEN
347 : WRITE (UNIT=output_unit, FMT="(/,T3,A,I4,A)") &
348 24 : "# Integrating the xc kernel on the atomic grids ..."
349 24 : CALL m_flush(output_unit)
350 : END IF
351 :
352 58 : CALL xas_atom_env_create(xas_atom_env)
353 58 : CALL init_xas_atom_env(xas_atom_env, xas_tdp_env, xas_tdp_control, qs_env)
354 58 : do_os = xas_tdp_control%do_uks .OR. xas_tdp_control%do_roks
355 :
356 58 : IF (xas_tdp_control%do_xc .AND. (.NOT. xas_tdp_control%xps_only)) THEN
357 48 : CALL integrate_fxc_atoms(xas_tdp_env%ri_fxc, xas_atom_env, xas_tdp_control, qs_env)
358 : END IF
359 :
360 58 : 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 58 : CALL xas_atom_env_release(xas_atom_env)
365 : END IF
366 :
367 : ! Compute the 3-center Coulomb integrals for the whole system
368 58 : 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 54 : IF (output_unit > 0) THEN
371 : WRITE (UNIT=output_unit, FMT="(/,T3,A,I4,A)") &
372 27 : "# Computing the RI 3-center Coulomb integrals ..."
373 27 : CALL m_flush(output_unit)
374 : END IF
375 54 : CALL compute_ri_3c_coulomb(xas_tdp_env, qs_env)
376 :
377 : END IF
378 :
379 : ! Loop over donor states for calculation
380 58 : CALL get_qs_env(qs_env=qs_env, atomic_kind_set=atomic_kind_set)
381 58 : current_state_index = 1
382 :
383 : ! Loop over atomic kinds
384 148 : DO ikind = 1, SIZE(atomic_kind_set)
385 :
386 90 : IF (xas_tdp_control%check_only) EXIT
387 124 : 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 64 : atom_list=atoms_of_kind)
391 :
392 : ! compute the RI coulomb2 inverse for this kind, and RI exchange2 if needed
393 64 : CALL compute_ri_coulomb2_int(ikind, xas_tdp_env, xas_tdp_control, qs_env)
394 64 : 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 64 : batch_size = 2
402 64 : CALL get_ri_3c_batches(ex_atoms_of_kind, nbatch, batch_size, atoms_of_kind, xas_tdp_env)
403 64 : nex_atom = SIZE(ex_atoms_of_kind)
404 :
405 : !Loop over batches
406 128 : DO ibatch = 1, nbatch
407 :
408 64 : bo = get_limit(nex_atom, nbatch, ibatch - 1)
409 64 : batch_size = bo(2) - bo(1) + 1
410 192 : ALLOCATE (batch_atoms(batch_size))
411 64 : iatom = 0
412 134 : DO iat = bo(1), bo(2)
413 70 : iatom = iatom + 1
414 134 : batch_atoms(iatom) = ex_atoms_of_kind(iat)
415 : END DO
416 64 : CALL sort_unique(batch_atoms, unique)
417 :
418 : !compute RI 3c exchange integrals on batch, if so required
419 64 : 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
430 134 : DO iat = 1, batch_size
431 70 : iatom = batch_atoms(iat)
432 :
433 70 : 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 70 : IF (xas_tdp_control%dipole_form == xas_dip_len .OR. xas_tdp_control%do_quad) THEN
438 24 : 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
442 150 : DO istate = 1, SIZE(xas_tdp_env%state_types, 1)
443 :
444 80 : IF (xas_tdp_env%state_types(istate, tmp_index) == xas_not_excited) CYCLE
445 :
446 80 : 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 80 : state_type=xas_tdp_env%state_types(istate, tmp_index))
450 :
451 : ! Initial write for the donor state of interest
452 80 : IF (output_unit > 0) THEN
453 : WRITE (UNIT=output_unit, FMT="(/,T3,A,A2,A,I4,A,A,/)") &
454 40 : "# Start of calculations for donor state of type ", &
455 40 : xas_tdp_env%state_type_char(current_state%state_type), " for atom", &
456 80 : current_state%at_index, " of kind ", TRIM(current_state%at_symbol)
457 40 : CALL m_flush(output_unit)
458 : END IF
459 :
460 : ! Assign best fitting MO(s) to current core donnor state
461 80 : 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 80 : CALL perform_mulliken_on_donor_state(current_state, qs_env)
465 :
466 : ! GW2X correction
467 80 : 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 80 : IF (.NOT. xas_tdp_control%xps_only) THEN
473 68 : CALL setup_xas_tdp_prob(current_state, qs_env, xas_tdp_env, xas_tdp_control)
474 :
475 68 : 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 8 : ex_type=tddfpt_spin_cons)
478 8 : CALL compute_dipole_fosc(current_state, xas_tdp_control, xas_tdp_env)
479 8 : 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 8 : xas_tdp_section, qs_env)
483 8 : CALL write_donor_state_restart(tddfpt_spin_cons, current_state, xas_tdp_section, qs_env)
484 : END IF
485 :
486 68 : 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 68 : 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 68 : 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 68 : 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 68 : CALL print_xas_tdp_to_file(current_state, xas_tdp_env, xas_tdp_control, xas_tdp_section)
527 : END IF !xps_only
528 80 : 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 80 : IF (.NOT. do_rixs) CALL free_ds_memory(current_state) ! donor-state will be cleaned in rixs
532 80 : current_state_index = current_state_index + 1
533 150 : NULLIFY (current_state)
534 :
535 : END DO ! state type
536 :
537 70 : end_of_batch = .FALSE.
538 70 : IF (iat == batch_size) end_of_batch = .TRUE.
539 134 : CALL free_exat_memory(xas_tdp_env, iatom, end_of_batch)
540 : END DO ! atom of batch
541 192 : DEALLOCATE (batch_atoms)
542 : END DO !ibatch
543 212 : DEALLOCATE (ex_atoms_of_kind)
544 : END DO ! kind
545 :
546 : ! Return to ususal KS matrix
547 58 : 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 58 : 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 58 : IF (.NOT. do_rixs) CALL xas_tdp_env_release(xas_tdp_env) ! is released at the end of rixs
565 58 : CALL xas_tdp_control_release(xas_tdp_control)
566 :
567 116 : 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 58 : 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 58 : INTEGER, DIMENSION(:), POINTER :: ind_of_kind
590 : LOGICAL :: do_os, do_rixs, do_uks, unique
591 : REAL(dp) :: fact
592 58 : REAL(dp), DIMENSION(:), POINTER :: mo_evals
593 : TYPE(admm_type), POINTER :: admm_env
594 58 : TYPE(atomic_kind_type), DIMENSION(:), POINTER :: at_kind_set
595 : TYPE(cell_type), POINTER :: cell
596 : TYPE(cp_fm_type), POINTER :: mo_coeff
597 58 : 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 58 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
602 58 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
603 58 : 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 58 : NULLIFY (xas_tdp_section, at_kind_set, ind_of_kind, dft_control, qs_kind_set, tmp_basis)
610 58 : NULLIFY (qs_loc_env, loc_section, mos, particle_set, rho, rho_ao, mo_evals, cell)
611 58 : NULLIFY (mo_coeff, matrix_ks, admm_env, dummy_section)
612 :
613 : ! XAS TDP control type initialization
614 58 : CALL get_qs_env(qs_env, dft_control=dft_control, do_rixs=do_rixs)
615 :
616 58 : IF (do_rixs) THEN
617 10 : 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 58 : CALL xas_tdp_control_create(xas_tdp_control)
623 58 : CALL read_xas_tdp_control(xas_tdp_control, xas_tdp_section)
624 :
625 : ! Check the qs_env for a LSD/ROKS calculation
626 58 : IF (dft_control%uks) xas_tdp_control%do_uks = .TRUE.
627 58 : IF (dft_control%roks) xas_tdp_control%do_roks = .TRUE.
628 58 : do_uks = xas_tdp_control%do_uks
629 58 : do_os = do_uks .OR. xas_tdp_control%do_roks
630 :
631 : ! XAS TDP environment type initialization
632 58 : IF (PRESENT(rixs_env)) THEN
633 10 : 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 58 : 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) .NE. 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 24 : 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 24 : CALL get_qs_env(qs_env=qs_env, atomic_kind_set=at_kind_set)
676 24 : n_kinds = SIZE(at_kind_set)
677 24 : nex_atoms = 0
678 :
679 24 : nex_kinds = SIZE(xas_tdp_control%list_ex_kinds)
680 72 : ALLOCATE (xas_tdp_env%ex_kind_indices(nex_kinds))
681 24 : k = 0
682 :
683 72 : DO i = 1, n_kinds
684 : CALL get_atomic_kind(atomic_kind=at_kind_set(i), name=kind_name, &
685 48 : natom=nat_of_kind, kind_number=kind_ind)
686 98 : IF (ANY(xas_tdp_control%list_ex_kinds == kind_name)) THEN
687 26 : nex_atoms = nex_atoms + nat_of_kind
688 26 : k = k + 1
689 26 : xas_tdp_env%ex_kind_indices(k) = kind_ind
690 : END IF
691 : END DO
692 :
693 72 : ALLOCATE (xas_tdp_env%ex_atom_indices(nex_atoms))
694 96 : ALLOCATE (xas_tdp_env%state_types(SIZE(xas_tdp_control%state_types, 1), nex_atoms))
695 24 : nex_atoms = 0
696 24 : nmatch = 0
697 :
698 72 : DO i = 1, n_kinds
699 : CALL get_atomic_kind(atomic_kind=at_kind_set(i), name=kind_name, &
700 48 : natom=nat_of_kind, atom_list=ind_of_kind)
701 126 : DO j = 1, nex_kinds
702 102 : IF (xas_tdp_control%list_ex_kinds(j) == kind_name) THEN
703 86 : xas_tdp_env%ex_atom_indices(nex_atoms + 1:nex_atoms + nat_of_kind) = ind_of_kind
704 62 : 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) = &
706 102 : xas_tdp_control%state_types(k, j)
707 : END DO
708 26 : nex_atoms = nex_atoms + nat_of_kind
709 26 : nmatch = nmatch + 1
710 : END IF
711 : END DO
712 : END DO
713 :
714 24 : 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 24 : IF (nmatch .NE. 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 58 : CALL sort_unique(xas_tdp_env%ex_atom_indices, unique)
725 58 : IF (.NOT. unique) THEN
726 0 : CPABORT("Excited atoms not uniquely defined.")
727 : END IF
728 :
729 : ! Check for periodicity
730 58 : CALL get_qs_env(qs_env, cell=cell)
731 184 : IF (ALL(cell%perd == 0)) THEN
732 42 : 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
740 208 : n_donor_states = COUNT(xas_tdp_env%state_types /= xas_not_excited)
741 254 : ALLOCATE (xas_tdp_env%donor_states(n_donor_states))
742 138 : DO i = 1, n_donor_states
743 138 : 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 58 : 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 58 : 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 58 : 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 58 : CALL create_localize_section(dummy_section)
782 58 : 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 58 : l_val=xas_tdp_control%do_loc)
785 58 : CALL section_release(dummy_section)
786 : xas_tdp_control%print_loc_subsection => section_vals_get_subs_vals( &
787 58 : xas_tdp_control%loc_subsection, "PRINT")
788 :
789 406 : ALLOCATE (xas_tdp_env%qs_loc_env)
790 58 : CALL qs_loc_env_create(xas_tdp_env%qs_loc_env)
791 58 : qs_loc_env => xas_tdp_env%qs_loc_env
792 58 : loc_section => xas_tdp_control%loc_subsection
793 : ! getting the number of MOs
794 58 : CALL get_qs_env(qs_env, mos=mos)
795 58 : CALL get_mo_set(mos(1), nmo=n_mo(1), homo=homo(1), nao=nao)
796 58 : n_mo(2) = n_mo(1)
797 58 : homo(2) = homo(1)
798 58 : nspins = 1
799 58 : IF (do_os) CALL get_mo_set(mos(2), nmo=n_mo(2), homo=homo(2))
800 58 : IF (do_uks) nspins = 2 !in roks, same MOs for both spins
801 :
802 : ! by default, all (doubly occupied) homo are localized
803 174 : 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 58 : nloc_xas=xas_tdp_control%n_search, spin_xas=1)
807 :
808 : ! do_xas argument above only prepares spin-alpha localization
809 58 : IF (do_uks) THEN
810 6 : qs_loc_env%localized_wfn_control%nloc_states(2) = xas_tdp_control%n_search
811 6 : qs_loc_env%localized_wfn_control%lu_bound_states(1, 2) = 1
812 6 : 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 58 : qs_loc_env%localized_wfn_control%operator_type = op_loc_berry
817 58 : qs_loc_env%localized_wfn_control%max_iter = 25000
818 58 : IF (.NOT. xas_tdp_control%do_loc) THEN
819 24 : 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
834 290 : 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 58 : IF (do_os) nspins = 2
838 58 : CALL get_qs_env(qs_env, rho=rho, matrix_s=matrix_s)
839 58 : CALL qs_rho_get(rho, rho_ao=rho_ao)
840 :
841 238 : ALLOCATE (xas_tdp_env%q_projector(nspins))
842 58 : ALLOCATE (xas_tdp_env%q_projector(1)%matrix)
843 : CALL dbcsr_create(xas_tdp_env%q_projector(1)%matrix, name="Q PROJECTOR ALPHA", &
844 58 : template=matrix_s(1)%matrix, matrix_type=dbcsr_type_no_symmetry)
845 58 : IF (do_os) THEN
846 6 : ALLOCATE (xas_tdp_env%q_projector(2)%matrix)
847 : CALL dbcsr_create(xas_tdp_env%q_projector(2)%matrix, name="Q PROJECTOR BETA", &
848 6 : 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 58 : 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 58 : xas_tdp_env%q_projector(1)%matrix, filter_eps=xas_tdp_control%eps_filter)
855 58 : CALL dbcsr_add_on_diag(xas_tdp_env%q_projector(1)%matrix, 1.0_dp)
856 58 : CALL dbcsr_finalize(xas_tdp_env%q_projector(1)%matrix)
857 :
858 58 : IF (do_os) THEN
859 : CALL dbcsr_multiply('N', 'N', fact, matrix_s(1)%matrix, rho_ao(2)%matrix, 0.0_dp, &
860 6 : xas_tdp_env%q_projector(2)%matrix, filter_eps=xas_tdp_control%eps_filter)
861 6 : CALL dbcsr_add_on_diag(xas_tdp_env%q_projector(2)%matrix, 1.0_dp)
862 6 : 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
866 232 : ALLOCATE (xas_tdp_env%dipmat(3))
867 232 : DO i = 1, 3
868 174 : ALLOCATE (xas_tdp_env%dipmat(i)%matrix)
869 174 : CALL dbcsr_copy(matrix_tmp, matrix_s(1)%matrix, name="XAS TDP dipole matrix")
870 174 : 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 54 : matrix_type=dbcsr_type_symmetric)
877 54 : CALL dbcsr_copy(xas_tdp_env%dipmat(i)%matrix, matrix_tmp)
878 : END IF
879 174 : CALL dbcsr_set(xas_tdp_env%dipmat(i)%matrix, 0.0_dp)
880 232 : CALL dbcsr_release(matrix_tmp)
881 : END DO
882 :
883 : ! Create the structure for the electric quadrupole in the AO basis, if required
884 58 : 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 58 : 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 58 : 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
903 124 : ALLOCATE (xas_tdp_env%orb_soc(i)%matrix)
904 : END DO
905 : END IF
906 :
907 : ! Check that everything is allowed
908 58 : CALL safety_check(xas_tdp_control, qs_env)
909 :
910 : ! Initialize libint for the 3-center integrals
911 58 : CALL cp_libint_static_init()
912 :
913 : ! Compute LUMOs as guess for OT solver and/or for GW2X correction
914 58 : 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 :
918 174 : 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 64 : 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 64 : TYPE(rng_stream_type), ALLOCATABLE :: rng_stream
938 :
939 : !Get the atoms from atoms_of_kind that are excited
940 64 : nex_atom = 0
941 292 : DO iat = 1, SIZE(atoms_of_kind)
942 228 : iatom = atoms_of_kind(iat)
943 458 : IF (.NOT. ANY(xas_tdp_env%ex_atom_indices == iatom)) CYCLE
944 292 : nex_atom = nex_atom + 1
945 : END DO
946 :
947 192 : ALLOCATE (ex_atoms_of_kind(nex_atom))
948 64 : nex_atom = 0
949 292 : DO iat = 1, SIZE(atoms_of_kind)
950 228 : iatom = atoms_of_kind(iat)
951 458 : IF (.NOT. ANY(xas_tdp_env%ex_atom_indices == iatom)) CYCLE
952 70 : nex_atom = nex_atom + 1
953 292 : ex_atoms_of_kind(nex_atom) = iatom
954 : END DO
955 :
956 : !We shuffle those atoms to spread them
957 64 : rng_stream = rng_stream_type(name="uniform_rng", distribution_type=UNIFORM)
958 64 : CALL rng_stream%shuffle(ex_atoms_of_kind(1:nex_atom))
959 :
960 64 : nbatch = nex_atom/batch_size
961 64 : IF (nbatch*batch_size .NE. nex_atom) nbatch = nbatch + 1
962 :
963 64 : 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 58 : 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 58 : .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 58 : IF (xas_tdp_control%do_roks .OR. xas_tdp_control%do_uks) THEN
985 :
986 6 : 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 6 : 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 6 : 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 58 : 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 58 : 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 58 : 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 58 : CALL get_qs_env(qs_env, dft_control=dft_control)
1045 58 : 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 58 : 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 58 : 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 58 : 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 58 : NULLIFY (input, kernel_section, dft_control, matrix_s)
1076 :
1077 58 : CALL get_qs_env(qs_env, input=input, dft_control=dft_control, matrix_s=matrix_s)
1078 :
1079 : !Overlap matrix sparsity
1080 58 : occ = dbcsr_get_occupation(matrix_s(1)%matrix)
1081 :
1082 58 : IF (ou .LE. 0) RETURN
1083 :
1084 : !Reference calculation
1085 29 : IF (xas_tdp_control%do_uks) THEN
1086 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1087 3 : "XAS_TDP| Reference calculation: Unrestricted Kohn-Sham"
1088 26 : ELSE IF (xas_tdp_control%do_roks) THEN
1089 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1090 0 : "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 29 : IF (xas_tdp_control%tamm_dancoff) THEN
1098 : WRITE (UNIT=ou, FMT="(T3,A)") &
1099 26 : "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 29 : 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 9 : "XAS_TDP| Transition Dipole Representation: LENGTH"
1112 : END IF
1113 :
1114 : !Quadrupole
1115 29 : 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 29 : 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 29 : "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 29 : "XAS_TDP| EPS_FILTER: ", xas_tdp_control%eps_filter
1132 :
1133 : !Grid info
1134 29 : IF (xas_tdp_control%do_xc) THEN
1135 : WRITE (UNIT=ou, FMT="(T3,A)") &
1136 24 : "XAS_TDP| Radial Grid(s) Info: Kind, na, nr"
1137 51 : DO i = 1, SIZE(xas_tdp_control%grid_info, 1)
1138 : WRITE (UNIT=ou, FMT="(T3,A,A6,A,A,A,A)") &
1139 27 : " ", TRIM(xas_tdp_control%grid_info(i, 1)), ", ", &
1140 78 : 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 29 : 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 29 : IF (xas_tdp_control%do_xc) THEN
1152 :
1153 : WRITE (UNIT=ou, FMT="(/,T3,A,F5.2,A)") &
1154 24 : "XAS_TDP| RI Region's Radius: ", xas_tdp_control%ri_radius*angstrom, " Ang"
1155 :
1156 : WRITE (UNIT=ou, FMT="(T3,A,/)") &
1157 24 : "XAS_TDP| XC Kernel Functional(s) used for the kernel:"
1158 :
1159 24 : kernel_section => section_vals_get_subs_vals(input, "DFT%XAS_TDP%KERNEL")
1160 24 : CALL xc_write(ou, kernel_section, lsd=.TRUE.)
1161 : END IF
1162 :
1163 : !HFX kernel
1164 29 : IF (xas_tdp_control%do_hfx) THEN
1165 : WRITE (UNIT=ou, FMT="(/,T3,A,/,/,T3,A,F5.3)") &
1166 22 : "XAS_TDP| Exact Exchange Kernel: Yes ", &
1167 44 : "EXACT_EXCHANGE| Scale: ", xas_tdp_control%sx
1168 22 : IF (xas_tdp_control%x_potential%potential_type == do_potential_coulomb) THEN
1169 : WRITE (UNIT=ou, FMT="(T3,A)") &
1170 15 : "EXACT_EXCHANGE| Potential : Coulomb"
1171 7 : ELSE IF (xas_tdp_control%x_potential%potential_type == do_potential_truncated) THEN
1172 : WRITE (UNIT=ou, FMT="(T3,A,/,T3,A,F5.2,A,/,T3,A,A)") &
1173 3 : "EXACT_EXCHANGE| Potential: Truncated Coulomb", &
1174 3 : "EXACT_EXCHANGE| Range: ", xas_tdp_control%x_potential%cutoff_radius*angstrom, ", (Ang)", &
1175 6 : "EXACT_EXCHANGE| T_C_G_DATA: ", TRIM(xas_tdp_control%x_potential%filename)
1176 4 : ELSE IF (xas_tdp_control%x_potential%potential_type == do_potential_short) THEN
1177 : WRITE (UNIT=ou, FMT="(T3,A,/,T3,A,F5.2,A,/,T3,A,F5.2,A,/,T3,A,ES7.1)") &
1178 4 : "EXACT_EXCHANGE| Potential: Short Range", &
1179 4 : "EXACT_EXCHANGE| Omega: ", xas_tdp_control%x_potential%omega, ", (1/a0)", &
1180 4 : "EXACT_EXCHANGE| Effective Range: ", xas_tdp_control%x_potential%cutoff_radius*angstrom, ", (Ang)", &
1181 8 : "EXACT_EXCHANGE| EPS_RANGE: ", xas_tdp_control%eps_range
1182 : END IF
1183 22 : IF (xas_tdp_control%eps_screen > 1.0E-16) THEN
1184 : WRITE (UNIT=ou, FMT="(T3,A,ES7.1)") &
1185 22 : "EXACT_EXCHANGE| EPS_SCREENING: ", xas_tdp_control%eps_screen
1186 : END IF
1187 :
1188 : !RI metric
1189 22 : IF (xas_tdp_control%do_ri_metric) THEN
1190 :
1191 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1192 3 : "EXACT_EXCHANGE| Using a RI metric"
1193 3 : IF (xas_tdp_control%ri_m_potential%potential_type == do_potential_id) THEN
1194 : WRITE (UNIT=ou, FMT="(T3,A)") &
1195 1 : "EXACT_EXCHANGE RI_METRIC| Potential : Overlap"
1196 2 : ELSE IF (xas_tdp_control%ri_m_potential%potential_type == do_potential_truncated) THEN
1197 : WRITE (UNIT=ou, FMT="(T3,A,/,T3,A,F5.2,A,/,T3,A,A)") &
1198 1 : "EXACT_EXCHANGE RI_METRIC| Potential: Truncated Coulomb", &
1199 1 : "EXACT_EXCHANGE RI_METRIC| Range: ", xas_tdp_control%ri_m_potential%cutoff_radius &
1200 1 : *angstrom, ", (Ang)", &
1201 2 : "EXACT_EXCHANGE RI_METRIC| T_C_G_DATA: ", TRIM(xas_tdp_control%ri_m_potential%filename)
1202 1 : ELSE IF (xas_tdp_control%ri_m_potential%potential_type == do_potential_short) THEN
1203 : WRITE (UNIT=ou, FMT="(T3,A,/,T3,A,F5.2,A,/,T3,A,F5.2,A,/,T3,A,ES7.1)") &
1204 1 : "EXACT_EXCHANGE RI_METRIC| Potential: Short Range", &
1205 1 : "EXACT_EXCHANGE RI_METRIC| Omega: ", xas_tdp_control%ri_m_potential%omega, ", (1/a0)", &
1206 1 : "EXACT_EXCHANGE RI_METRIC| Effective Range: ", &
1207 1 : xas_tdp_control%ri_m_potential%cutoff_radius*angstrom, ", (Ang)", &
1208 2 : "EXACT_EXCHANGE RI_METRIC| EPS_RANGE: ", xas_tdp_control%eps_range
1209 : END IF
1210 : END IF
1211 : ELSE
1212 : WRITE (UNIT=ou, FMT="(/,T3,A,/)") &
1213 7 : "XAS_TDP| Exact Exchange Kernel: No "
1214 : END IF
1215 :
1216 : !overlap mtrix occupation
1217 : WRITE (UNIT=ou, FMT="(/,T3,A,F5.2)") &
1218 29 : "XAS_TDP| Overlap matrix occupation: ", occ
1219 :
1220 : !GW2X parameter
1221 29 : IF (xas_tdp_control%do_gw2x) THEN
1222 : WRITE (UNIT=ou, FMT="(T3,A,/)") &
1223 9 : "XAS_TDP| GW2X correction enabled"
1224 :
1225 9 : IF (xas_tdp_control%xps_only) THEN
1226 : WRITE (UNIT=ou, FMT="(T3,A)") &
1227 2 : "GW2X| Only computing ionizations potentials for XPS"
1228 : END IF
1229 :
1230 9 : IF (xas_tdp_control%pseudo_canonical) THEN
1231 : WRITE (UNIT=ou, FMT="(T3,A)") &
1232 8 : "GW2X| Using the pseudo-canonical scheme"
1233 : ELSE
1234 : WRITE (UNIT=ou, FMT="(T3,A)") &
1235 1 : "GW2X| Using the GW2X* scheme"
1236 : END IF
1237 :
1238 : WRITE (UNIT=ou, FMT="(T3,A,ES7.1)") &
1239 9 : "GW2X| EPS_GW2X: ", xas_tdp_control%gw2x_eps
1240 :
1241 : WRITE (UNIT=ou, FMT="(T3,A,I5)") &
1242 9 : "GW2X| contraction batch size: ", xas_tdp_control%batch_size
1243 :
1244 9 : IF ((INT(xas_tdp_control%c_os) .NE. 1) .OR. (INT(xas_tdp_control%c_ss) .NE. 1)) THEN
1245 : WRITE (UNIT=ou, FMT="(T3,A,F7.4,/,T3,A,F7.4)") &
1246 1 : "GW2X| Same-spin scaling factor: ", xas_tdp_control%c_ss, &
1247 2 : "GW2X| Opposite-spin scaling factor: ", xas_tdp_control%c_os
1248 : END IF
1249 :
1250 : END IF
1251 :
1252 58 : END SUBROUTINE print_info
1253 :
1254 : ! **************************************************************************************************
1255 : !> \brief Assosciate (possibly localized) lowest energy MOs to each excited atoms. The procedure
1256 : !> looks for MOs "centered" on the excited atoms by comparing distances. It
1257 : !> then fills the mos_of_ex_atoms arrays of the xas_tdp_env. Only the xas_tdp_control%n_search
1258 : !> lowest energy MOs are considered. Largely inspired by MI's implementation of XAS
1259 : !> It is assumed that the Berry phase is used to compute centers.
1260 : !> \param xas_tdp_env ...
1261 : !> \param xas_tdp_control ...
1262 : !> \param qs_env ...
1263 : !> \note Whether localization took place or not, the procedure is the same as centers are stored in
1264 : !> xas_tdp_env%qs_loc_env%localized_wfn_control%centers_set
1265 : !> Assumes that find_mo_centers has been run previously
1266 : ! **************************************************************************************************
1267 58 : SUBROUTINE assign_mos_to_ex_atoms(xas_tdp_env, xas_tdp_control, qs_env)
1268 :
1269 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1270 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1271 : TYPE(qs_environment_type), POINTER :: qs_env
1272 :
1273 : INTEGER :: at_index, iat, iat_memo, imo, ispin, &
1274 : n_atoms, n_search, nex_atoms, nspins
1275 : INTEGER, DIMENSION(3) :: perd_init
1276 58 : INTEGER, DIMENSION(:, :, :), POINTER :: mos_of_ex_atoms
1277 : REAL(dp) :: dist, dist_min
1278 : REAL(dp), DIMENSION(3) :: at_pos, r_ac, wfn_center
1279 : TYPE(cell_type), POINTER :: cell
1280 : TYPE(localized_wfn_control_type), POINTER :: localized_wfn_control
1281 58 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
1282 :
1283 58 : NULLIFY (localized_wfn_control, mos_of_ex_atoms, cell, particle_set)
1284 :
1285 : ! Initialization. mos_of_ex_atoms filled with -1, meaning no assigned state
1286 58 : mos_of_ex_atoms => xas_tdp_env%mos_of_ex_atoms
1287 580 : mos_of_ex_atoms(:, :, :) = -1
1288 58 : n_search = xas_tdp_control%n_search
1289 58 : nex_atoms = xas_tdp_env%nex_atoms
1290 58 : localized_wfn_control => xas_tdp_env%qs_loc_env%localized_wfn_control
1291 58 : CALL get_qs_env(qs_env=qs_env, particle_set=particle_set, cell=cell)
1292 58 : n_atoms = SIZE(particle_set)
1293 58 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
1294 :
1295 : ! Temporarly impose periodic BCs because of Berry's phase operator used for localization
1296 232 : perd_init = cell%perd
1297 232 : cell%perd = 1
1298 :
1299 : ! Loop over n_search lowest energy MOs and all atoms, for each spin
1300 122 : DO ispin = 1, nspins
1301 414 : DO imo = 1, n_search
1302 : ! retrieve MO wave function center coordinates.
1303 1168 : wfn_center(1:3) = localized_wfn_control%centers_set(ispin)%array(1:3, imo)
1304 292 : iat_memo = 0
1305 :
1306 : ! a large enough value to avoid bad surprises
1307 292 : dist_min = 10000.0_dp
1308 7678 : DO iat = 1, n_atoms
1309 29544 : at_pos = particle_set(iat)%r
1310 7386 : r_ac = pbc(at_pos, wfn_center, cell)
1311 29544 : dist = NORM2(r_ac)
1312 :
1313 : ! keep memory of which atom is the closest to the wave function center
1314 7678 : IF (dist < dist_min) THEN
1315 668 : iat_memo = iat
1316 668 : dist_min = dist
1317 : END IF
1318 : END DO
1319 :
1320 : ! Verify that the closest atom is actually excited and assign the MO if so
1321 588 : IF (ANY(xas_tdp_env%ex_atom_indices == iat_memo)) THEN
1322 134 : at_index = locate(xas_tdp_env%ex_atom_indices, iat_memo)
1323 134 : mos_of_ex_atoms(imo, at_index, ispin) = 1
1324 : END IF
1325 : END DO !imo
1326 : END DO !ispin
1327 :
1328 : ! Go back to initial BCs
1329 232 : cell%perd = perd_init
1330 :
1331 58 : END SUBROUTINE assign_mos_to_ex_atoms
1332 :
1333 : ! **************************************************************************************************
1334 : !> \brief Re-initialize the qs_loc_env to the current MOs.
1335 : !> \param qs_loc_env the env to re-initialize
1336 : !> \param n_loc_states the number of states to include
1337 : !> \param do_uks in cas of spin unrestricted calculation, initialize for both spins
1338 : !> \param qs_env ...
1339 : !> \note Useful when one needs to make use of qs_loc features and it is either with canonical MOs
1340 : !> or the localized MOs have been modified. do_localize is overwritten.
1341 : !> Same loc range for both spins
1342 : ! **************************************************************************************************
1343 92 : SUBROUTINE reinit_qs_loc_env(qs_loc_env, n_loc_states, do_uks, qs_env)
1344 :
1345 : TYPE(qs_loc_env_type), POINTER :: qs_loc_env
1346 : INTEGER, INTENT(IN) :: n_loc_states
1347 : LOGICAL, INTENT(IN) :: do_uks
1348 : TYPE(qs_environment_type), POINTER :: qs_env
1349 :
1350 : INTEGER :: i, nspins
1351 : TYPE(localized_wfn_control_type), POINTER :: loc_wfn_control
1352 :
1353 : ! First, release the old env
1354 92 : CALL qs_loc_env_release(qs_loc_env)
1355 :
1356 : ! Re-create it
1357 92 : CALL qs_loc_env_create(qs_loc_env)
1358 92 : CALL localized_wfn_control_create(qs_loc_env%localized_wfn_control)
1359 92 : loc_wfn_control => qs_loc_env%localized_wfn_control
1360 :
1361 : ! Initialize it
1362 92 : loc_wfn_control%localization_method = do_loc_none
1363 92 : loc_wfn_control%operator_type = op_loc_berry
1364 276 : loc_wfn_control%nloc_states(:) = n_loc_states
1365 92 : loc_wfn_control%eps_occ = 0.0_dp
1366 276 : loc_wfn_control%lu_bound_states(1, :) = 1
1367 276 : loc_wfn_control%lu_bound_states(2, :) = n_loc_states
1368 92 : loc_wfn_control%set_of_states = state_loc_list
1369 92 : loc_wfn_control%do_homo = .TRUE.
1370 276 : ALLOCATE (loc_wfn_control%loc_states(n_loc_states, 2))
1371 584 : DO i = 1, n_loc_states
1372 1568 : loc_wfn_control%loc_states(i, :) = i
1373 : END DO
1374 :
1375 92 : nspins = 1; IF (do_uks) nspins = 2
1376 92 : CALL set_loc_centers(loc_wfn_control, loc_wfn_control%nloc_states, nspins=nspins)
1377 : ! need to set do_localize=.TRUE. because otherwise no routine works
1378 92 : IF (do_uks) THEN
1379 8 : CALL qs_loc_env_init(qs_loc_env, loc_wfn_control, qs_env, do_localize=.TRUE.)
1380 : ELSE
1381 84 : CALL qs_loc_env_init(qs_loc_env, loc_wfn_control, qs_env, myspin=1, do_localize=.TRUE.)
1382 : END IF
1383 :
1384 92 : END SUBROUTINE reinit_qs_loc_env
1385 :
1386 : ! *************************************************************************************************
1387 : !> \brief Diagonalize the subset of previously localized MOs that are associated to each excited
1388 : !> atoms. Updates the MO coeffs accordingly.
1389 : !> \param xas_tdp_env ...
1390 : !> \param xas_tdp_control ...
1391 : !> \param qs_env ...
1392 : !> \note Needed because after localization, the MOs loose their identity (1s, 2s , 2p, etc)
1393 : ! **************************************************************************************************
1394 34 : SUBROUTINE diagonalize_assigned_mo_subset(xas_tdp_env, xas_tdp_control, qs_env)
1395 :
1396 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1397 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1398 : TYPE(qs_environment_type), POINTER :: qs_env
1399 :
1400 : INTEGER :: i, iat, ilmo, ispin, nao, nlmo, nspins
1401 34 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: evals
1402 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
1403 : TYPE(cp_fm_struct_type), POINTER :: ks_struct, lmo_struct
1404 : TYPE(cp_fm_type) :: evecs, ks_fm, lmo_fm, work
1405 : TYPE(cp_fm_type), POINTER :: mo_coeff
1406 34 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks
1407 34 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
1408 : TYPE(mp_para_env_type), POINTER :: para_env
1409 :
1410 34 : NULLIFY (mos, mo_coeff, matrix_ks, para_env, blacs_env, lmo_struct, ks_struct)
1411 :
1412 : ! Get what we need from qs_env
1413 34 : CALL get_qs_env(qs_env, mos=mos, matrix_ks=matrix_ks, para_env=para_env, blacs_env=blacs_env)
1414 :
1415 34 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
1416 :
1417 : ! Loop over the excited atoms and spin
1418 70 : DO ispin = 1, nspins
1419 116 : DO iat = 1, xas_tdp_env%nex_atoms
1420 :
1421 : ! get the MOs
1422 46 : CALL get_mo_set(mos(ispin), mo_coeff=mo_coeff, nao=nao)
1423 :
1424 : ! count how many MOs are associated to this atom and create a fm/struct
1425 346 : nlmo = COUNT(xas_tdp_env%mos_of_ex_atoms(:, iat, ispin) == 1)
1426 : CALL cp_fm_struct_create(lmo_struct, nrow_global=nao, ncol_global=nlmo, &
1427 46 : para_env=para_env, context=blacs_env)
1428 46 : CALL cp_fm_create(lmo_fm, lmo_struct)
1429 46 : CALL cp_fm_create(work, lmo_struct)
1430 :
1431 : CALL cp_fm_struct_create(ks_struct, nrow_global=nlmo, ncol_global=nlmo, &
1432 46 : para_env=para_env, context=blacs_env)
1433 46 : CALL cp_fm_create(ks_fm, ks_struct)
1434 46 : CALL cp_fm_create(evecs, ks_struct)
1435 :
1436 : ! Loop over the localized MOs associated to this atom
1437 46 : i = 0
1438 346 : DO ilmo = 1, xas_tdp_control%n_search
1439 300 : IF (xas_tdp_env%mos_of_ex_atoms(ilmo, iat, ispin) == -1) CYCLE
1440 :
1441 62 : i = i + 1
1442 : ! put the coeff in our atom-restricted lmo_fm
1443 : CALL cp_fm_to_fm_submat(mo_coeff, lmo_fm, nrow=nao, ncol=1, s_firstrow=1, &
1444 346 : s_firstcol=ilmo, t_firstrow=1, t_firstcol=i)
1445 :
1446 : END DO !ilmo
1447 :
1448 : ! Computing the KS matrix in the subset of MOs
1449 46 : CALL cp_dbcsr_sm_fm_multiply(matrix_ks(ispin)%matrix, lmo_fm, work, ncol=nlmo)
1450 46 : CALL parallel_gemm('T', 'N', nlmo, nlmo, nao, 1.0_dp, lmo_fm, work, 0.0_dp, ks_fm)
1451 :
1452 : ! Diagonalizing the KS matrix in the subset of MOs
1453 138 : ALLOCATE (evals(nlmo))
1454 46 : CALL cp_fm_syevd(ks_fm, evecs, evals)
1455 46 : DEALLOCATE (evals)
1456 :
1457 : ! Express the MOs in the basis that diagonalizes KS
1458 46 : CALL parallel_gemm('N', 'N', nao, nlmo, nlmo, 1.0_dp, lmo_fm, evecs, 0.0_dp, work)
1459 :
1460 : ! Replacing the new MOs back in the MO coeffs
1461 46 : i = 0
1462 346 : DO ilmo = 1, xas_tdp_control%n_search
1463 300 : IF (xas_tdp_env%mos_of_ex_atoms(ilmo, iat, ispin) == -1) CYCLE
1464 :
1465 62 : i = i + 1
1466 : CALL cp_fm_to_fm_submat(work, mo_coeff, nrow=nao, ncol=1, s_firstrow=1, &
1467 346 : s_firstcol=i, t_firstrow=1, t_firstcol=ilmo)
1468 :
1469 : END DO
1470 :
1471 : ! Excited atom clean-up
1472 46 : CALL cp_fm_release(lmo_fm)
1473 46 : CALL cp_fm_release(work)
1474 46 : CALL cp_fm_struct_release(lmo_struct)
1475 46 : CALL cp_fm_release(ks_fm)
1476 46 : CALL cp_fm_release(evecs)
1477 220 : CALL cp_fm_struct_release(ks_struct)
1478 : END DO !iat
1479 : END DO !ispin
1480 :
1481 68 : END SUBROUTINE diagonalize_assigned_mo_subset
1482 :
1483 : ! **************************************************************************************************
1484 : !> \brief Assign core MO(s) to a given donor_state, taking the type (1S, 2S, etc) into account.
1485 : !> The projection on a representative Slater-type orbital basis is used as a indicator.
1486 : !> It is assumed that MOs are already assigned to excited atoms based on their center
1487 : !> \param donor_state the donor_state to which a MO must be assigned
1488 : !> \param xas_tdp_env ...
1489 : !> \param xas_tdp_control ...
1490 : !> \param qs_env ...
1491 : ! **************************************************************************************************
1492 80 : SUBROUTINE assign_mos_to_donor_state(donor_state, xas_tdp_env, xas_tdp_control, qs_env)
1493 :
1494 : TYPE(donor_state_type), POINTER :: donor_state
1495 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1496 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1497 : TYPE(qs_environment_type), POINTER :: qs_env
1498 :
1499 : INTEGER :: at_index, i, iat, imo, ispin, l, my_mo, &
1500 : n_search, n_states, nao, ndo_so, nj, &
1501 : nsgf_kind, nsgf_sto, nspins, &
1502 : output_unit, zval
1503 80 : INTEGER, ALLOCATABLE, DIMENSION(:, :) :: my_mos
1504 : INTEGER, DIMENSION(2) :: next_best_overlap_ind
1505 : INTEGER, DIMENSION(4, 7) :: ne
1506 80 : INTEGER, DIMENSION(:), POINTER :: first_sgf, lq, nq
1507 80 : INTEGER, DIMENSION(:, :, :), POINTER :: mos_of_ex_atoms
1508 : LOGICAL :: unique
1509 : REAL(dp) :: zeff
1510 80 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: diag, overlap, sto_overlap
1511 80 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: max_overlap
1512 : REAL(dp), DIMENSION(2) :: next_best_overlap
1513 80 : REAL(dp), DIMENSION(:), POINTER :: mo_evals, zeta
1514 80 : REAL(dp), DIMENSION(:, :), POINTER :: overlap_matrix, tmp_coeff
1515 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
1516 : TYPE(cp_fm_struct_type), POINTER :: eval_mat_struct, gs_struct, matrix_struct
1517 : TYPE(cp_fm_type) :: eval_mat, work_mat
1518 : TYPE(cp_fm_type), POINTER :: gs_coeffs, mo_coeff
1519 80 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks
1520 : TYPE(gto_basis_set_type), POINTER :: kind_basis_set, sto_to_gto_basis_set
1521 80 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
1522 : TYPE(mp_para_env_type), POINTER :: para_env
1523 80 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
1524 80 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
1525 : TYPE(sto_basis_set_type), POINTER :: sto_basis_set
1526 :
1527 80 : NULLIFY (sto_basis_set, sto_to_gto_basis_set, qs_kind_set, kind_basis_set, lq, nq, zeta)
1528 80 : NULLIFY (overlap_matrix, mos, mo_coeff, mos_of_ex_atoms, tmp_coeff, first_sgf, particle_set)
1529 80 : NULLIFY (mo_evals, matrix_ks, para_env, blacs_env)
1530 80 : NULLIFY (eval_mat_struct, gs_struct, gs_coeffs)
1531 :
1532 160 : output_unit = cp_logger_get_default_io_unit()
1533 :
1534 : CALL get_qs_env(qs_env=qs_env, qs_kind_set=qs_kind_set, mos=mos, particle_set=particle_set, &
1535 80 : matrix_ks=matrix_ks, para_env=para_env, blacs_env=blacs_env)
1536 :
1537 80 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
1538 :
1539 : ! Construction of a STO that fits the type of orbital we look for
1540 80 : ALLOCATE (zeta(1))
1541 80 : ALLOCATE (lq(1))
1542 80 : ALLOCATE (nq(1))
1543 : ! Retrieving quantum numbers
1544 80 : IF (donor_state%state_type == xas_1s_type) THEN
1545 66 : nq(1) = 1
1546 66 : lq(1) = 0
1547 66 : n_states = 1
1548 14 : ELSE IF (donor_state%state_type == xas_2s_type) THEN
1549 6 : nq(1) = 2
1550 6 : lq(1) = 0
1551 6 : n_states = 1
1552 8 : ELSE IF (donor_state%state_type == xas_2p_type) THEN
1553 8 : nq(1) = 2
1554 8 : lq(1) = 1
1555 8 : n_states = 3
1556 : ELSE
1557 0 : CPABORT("Procedure for required type not implemented")
1558 : END IF
1559 320 : ALLOCATE (my_mos(n_states, nspins))
1560 240 : ALLOCATE (max_overlap(n_states, nspins))
1561 :
1562 : ! Getting the atomic number
1563 80 : CALL get_qs_kind(qs_kind_set(donor_state%kind_index), zeff=zeff)
1564 80 : zval = INT(zeff)
1565 :
1566 : ! Electronic configuration (copied from MI's XAS)
1567 80 : ne = 0
1568 400 : DO l = 1, 4
1569 320 : nj = 2*(l - 1) + 1
1570 2160 : DO i = l, 7
1571 1760 : ne(l, i) = ptable(zval)%e_conv(l - 1) - 2*nj*(i - l)
1572 1760 : ne(l, i) = MAX(ne(l, i), 0)
1573 2080 : ne(l, i) = MIN(ne(l, i), 2*nj)
1574 : END DO
1575 : END DO
1576 :
1577 : ! computing zeta with the Slater sum rules
1578 80 : zeta(1) = srules(zval, ne, nq(1), lq(1))
1579 :
1580 : ! Allocating memory and initiate STO
1581 80 : CALL allocate_sto_basis_set(sto_basis_set)
1582 80 : CALL set_sto_basis_set(sto_basis_set, nshell=1, nq=nq, lq=lq, zet=zeta)
1583 :
1584 : ! Some clean-up
1585 80 : DEALLOCATE (nq, lq, zeta)
1586 :
1587 : ! Expanding the STO into (normalized) GTOs for later calculations, use standard 3 gaussians
1588 : CALL create_gto_from_sto_basis(sto_basis_set=sto_basis_set, &
1589 : gto_basis_set=sto_to_gto_basis_set, &
1590 80 : ngauss=3)
1591 80 : sto_to_gto_basis_set%norm_type = 2
1592 80 : CALL init_orb_basis_set(sto_to_gto_basis_set)
1593 :
1594 : ! Retrieving the atomic kind related GTO in which MOs are expanded
1595 80 : CALL get_qs_kind(qs_kind_set(donor_state%kind_index), basis_set=kind_basis_set)
1596 :
1597 : ! Allocating and computing the overlap between the two basis (they share the same center)
1598 80 : CALL get_gto_basis_set(gto_basis_set=kind_basis_set, nsgf=nsgf_kind)
1599 80 : CALL get_gto_basis_set(gto_basis_set=sto_to_gto_basis_set, nsgf=nsgf_sto)
1600 320 : ALLOCATE (overlap_matrix(nsgf_sto, nsgf_kind))
1601 :
1602 : ! Making use of MI's subroutine
1603 80 : CALL calc_stogto_overlap(sto_to_gto_basis_set, kind_basis_set, overlap_matrix)
1604 :
1605 : ! Some clean-up
1606 80 : CALL deallocate_sto_basis_set(sto_basis_set)
1607 80 : CALL deallocate_gto_basis_set(sto_to_gto_basis_set)
1608 :
1609 : ! Looping over the potential donor states to compute overlap with STO basis
1610 80 : mos_of_ex_atoms => xas_tdp_env%mos_of_ex_atoms
1611 80 : n_search = xas_tdp_control%n_search
1612 80 : at_index = donor_state%at_index
1613 80 : iat = locate(xas_tdp_env%ex_atom_indices, at_index)
1614 240 : ALLOCATE (first_sgf(SIZE(particle_set))) !probably do not need that
1615 80 : CALL get_particle_set(particle_set=particle_set, qs_kind_set=qs_kind_set, first_sgf=first_sgf)
1616 240 : ALLOCATE (tmp_coeff(nsgf_kind, 1))
1617 160 : ALLOCATE (sto_overlap(nsgf_kind))
1618 240 : ALLOCATE (overlap(n_search))
1619 :
1620 80 : next_best_overlap = 0.0_dp
1621 276 : max_overlap = 0.0_dp
1622 :
1623 168 : DO ispin = 1, nspins
1624 :
1625 88 : CALL get_mo_set(mos(ispin), mo_coeff=mo_coeff, nao=nao)
1626 518 : overlap = 0.0_dp
1627 :
1628 88 : my_mo = 0
1629 518 : DO imo = 1, n_search
1630 518 : IF (mos_of_ex_atoms(imo, iat, ispin) > 0) THEN
1631 :
1632 4320 : sto_overlap = 0.0_dp
1633 4504 : tmp_coeff = 0.0_dp
1634 :
1635 : ! Getting the relevant coefficients for the candidate state
1636 : CALL cp_fm_get_submatrix(fm=mo_coeff, target_m=tmp_coeff, start_row=first_sgf(at_index), &
1637 184 : start_col=imo, n_rows=nsgf_kind, n_cols=1, transpose=.FALSE.)
1638 :
1639 : ! Computing the product overlap_matrix*coeffs
1640 : CALL dgemm('N', 'N', nsgf_sto, 1, nsgf_kind, 1.0_dp, overlap_matrix, nsgf_sto, &
1641 184 : tmp_coeff, nsgf_kind, 0.0_dp, sto_overlap, nsgf_sto)
1642 :
1643 : ! Each element of column vector sto_overlap is the overlap of a basis element of the
1644 : ! generated STO basis with the kind specific orbital basis. Take the sum of the absolute
1645 : ! values so that rotation (of the px, py, pz for example) does not hinder our search
1646 4320 : overlap(imo) = SUM(ABS(sto_overlap))
1647 :
1648 : END IF
1649 : END DO
1650 :
1651 : ! Finding the best overlap(s)
1652 196 : DO i = 1, n_states
1653 638 : my_mo = MAXLOC(overlap, 1)
1654 108 : my_mos(i, ispin) = my_mo
1655 746 : max_overlap(i, ispin) = MAXVAL(overlap, 1)
1656 196 : overlap(my_mo) = 0.0_dp
1657 : END DO
1658 : ! Getting the next best overlap (for validation purposes)
1659 606 : next_best_overlap(ispin) = MAXVAL(overlap, 1)
1660 518 : next_best_overlap_ind(ispin) = MAXLOC(overlap, 1)
1661 :
1662 : ! Sort MO indices
1663 256 : CALL sort_unique(my_mos(:, ispin), unique)
1664 :
1665 : END DO !ispin
1666 :
1667 : ! Some clean-up
1668 80 : DEALLOCATE (overlap_matrix, tmp_coeff)
1669 :
1670 : ! Dealing with the result
1671 552 : IF (ALL(my_mos > 0) .AND. ALL(my_mos <= n_search)) THEN
1672 : ! Assigning the MO indices to the donor_state
1673 160 : ALLOCATE (donor_state%mo_indices(n_states, nspins))
1674 276 : donor_state%mo_indices = my_mos
1675 80 : donor_state%ndo_mo = n_states
1676 :
1677 : ! Storing the MOs in the donor_state, as vectors column: first columns alpha spin, then beta
1678 : CALL cp_fm_struct_create(gs_struct, nrow_global=nao, ncol_global=n_states*nspins, &
1679 80 : para_env=para_env, context=blacs_env)
1680 80 : ALLOCATE (donor_state%gs_coeffs)
1681 80 : CALL cp_fm_create(donor_state%gs_coeffs, gs_struct)
1682 :
1683 80 : IF (.NOT. ASSOCIATED(xas_tdp_env%mo_coeff)) THEN
1684 180 : ALLOCATE (xas_tdp_env%mo_coeff(nspins))
1685 : END IF
1686 :
1687 168 : DO ispin = 1, nspins
1688 88 : CALL get_mo_set(mos(ispin), mo_coeff=mo_coeff)
1689 : ! check if mo_coeff is copied before for another donor_state
1690 88 : IF (.NOT. ASSOCIATED(xas_tdp_env%mo_coeff(ispin)%local_data)) THEN
1691 : ! copy mo_coeff
1692 : CALL cp_fm_get_info(matrix=mo_coeff, &
1693 64 : matrix_struct=matrix_struct)
1694 64 : CALL cp_fm_create(xas_tdp_env%mo_coeff(ispin), matrix_struct)
1695 64 : CALL cp_fm_to_fm(mo_coeff, xas_tdp_env%mo_coeff(ispin))
1696 : END IF
1697 :
1698 276 : DO i = 1, n_states
1699 : CALL cp_fm_to_fm_submat(msource=mo_coeff, mtarget=donor_state%gs_coeffs, nrow=nao, &
1700 : ncol=1, s_firstrow=1, s_firstcol=my_mos(i, ispin), &
1701 196 : t_firstrow=1, t_firstcol=(ispin - 1)*n_states + i)
1702 : END DO
1703 : END DO
1704 80 : gs_coeffs => donor_state%gs_coeffs
1705 :
1706 : !Keep the subset of the coeffs centered on the excited atom as global array (used a lot)
1707 320 : ALLOCATE (donor_state%contract_coeffs(nsgf_kind, n_states*nspins))
1708 : CALL cp_fm_get_submatrix(gs_coeffs, donor_state%contract_coeffs, start_row=first_sgf(at_index), &
1709 80 : start_col=1, n_rows=nsgf_kind, n_cols=n_states*nspins)
1710 :
1711 : ! Assigning corresponding energy eigenvalues and writing some info in standard input file
1712 :
1713 : !standard eigenvalues as gotten from the KS diagonalization in the ground state
1714 80 : IF (.NOT. xas_tdp_control%do_loc .AND. .NOT. xas_tdp_control%do_roks) THEN
1715 30 : IF (output_unit > 0) THEN
1716 : WRITE (UNIT=output_unit, FMT="(T5,A,/,T5,A,/,T5,A)") &
1717 15 : "The following canonical MO(s) have been associated with the donor state(s)", &
1718 15 : "based on the overlap with the components of a minimal STO basis: ", &
1719 30 : " Spin MO index overlap(sum)"
1720 : END IF
1721 :
1722 60 : ALLOCATE (donor_state%energy_evals(n_states, nspins))
1723 110 : donor_state%energy_evals = 0.0_dp
1724 :
1725 : ! Canonical MO, no change in eigenvalues, only diagonal elements
1726 64 : DO ispin = 1, nspins
1727 34 : CALL get_mo_set(mos(ispin), eigenvalues=mo_evals)
1728 110 : DO i = 1, n_states
1729 46 : donor_state%energy_evals(i, ispin) = mo_evals(my_mos(i, ispin))
1730 :
1731 80 : IF (output_unit > 0) THEN
1732 : WRITE (UNIT=output_unit, FMT="(T46,I4,I11,F17.5)") &
1733 23 : ispin, my_mos(i, ispin), max_overlap(i, ispin)
1734 : END IF
1735 : END DO
1736 : END DO
1737 :
1738 : !either localization of MOs or ROKS, in both cases the MO eigenvalues from the KS
1739 : !digonalization mat have changed
1740 : ELSE
1741 50 : IF (output_unit > 0) THEN
1742 : WRITE (UNIT=output_unit, FMT="(T5,A,/,T5,A,/,T5,A)") &
1743 25 : "The following localized MO(s) have been associated with the donor state(s)", &
1744 25 : "based on the overlap with the components of a minimal STO basis: ", &
1745 50 : " Spin MO index overlap(sum)"
1746 : END IF
1747 :
1748 : ! Loop over the donor states and print
1749 104 : DO ispin = 1, nspins
1750 166 : DO i = 1, n_states
1751 :
1752 : ! Print info
1753 116 : IF (output_unit > 0) THEN
1754 : WRITE (UNIT=output_unit, FMT="(T46,I4,I11,F17.5)") &
1755 31 : ispin, my_mos(i, ispin), max_overlap(i, ispin)
1756 : END IF
1757 : END DO
1758 : END DO
1759 :
1760 : ! MO have been rotated or non-physical ROKS MO eigrenvalues:
1761 : ! => need epsilon_ij = <psi_i|F|psi_j> = sum_{pq} c_{qi}c_{pj} F_{pq}
1762 : ! Note: only have digonal elements by construction
1763 50 : ndo_so = nspins*n_states
1764 50 : CALL cp_fm_create(work_mat, gs_struct)
1765 : CALL cp_fm_struct_create(eval_mat_struct, nrow_global=ndo_so, ncol_global=ndo_so, &
1766 50 : para_env=para_env, context=blacs_env)
1767 50 : CALL cp_fm_create(eval_mat, eval_mat_struct)
1768 150 : ALLOCATE (diag(ndo_so))
1769 :
1770 50 : IF (.NOT. xas_tdp_control%do_roks) THEN
1771 :
1772 100 : ALLOCATE (donor_state%energy_evals(n_states, nspins))
1773 166 : donor_state%energy_evals = 0.0_dp
1774 :
1775 : ! Compute gs_coeff^T * matrix_ks * gs_coeff to get the epsilon_ij matrix
1776 104 : DO ispin = 1, nspins
1777 54 : CALL cp_dbcsr_sm_fm_multiply(matrix_ks(ispin)%matrix, gs_coeffs, work_mat, ncol=ndo_so)
1778 54 : CALL parallel_gemm('T', 'N', ndo_so, ndo_so, nao, 1.0_dp, gs_coeffs, work_mat, 0.0_dp, eval_mat)
1779 :
1780 : ! Put the epsilon_ii into the donor_state. No off-diagonal element because of subset diag
1781 54 : CALL cp_fm_get_diag(eval_mat, diag)
1782 166 : donor_state%energy_evals(:, ispin) = diag((ispin - 1)*n_states + 1:ispin*n_states)
1783 :
1784 : END DO
1785 :
1786 : ELSE
1787 : ! If ROKS, slightly different procedure => 2 KS matrices but one type of MOs
1788 0 : ALLOCATE (donor_state%energy_evals(n_states, 2))
1789 0 : donor_state%energy_evals = 0.0_dp
1790 :
1791 : ! Compute gs_coeff^T * matrix_ks * gs_coeff to get the epsilon_ij matrix
1792 0 : DO ispin = 1, 2
1793 0 : CALL cp_dbcsr_sm_fm_multiply(matrix_ks(ispin)%matrix, gs_coeffs, work_mat, ncol=ndo_so)
1794 0 : CALL parallel_gemm('T', 'N', ndo_so, ndo_so, nao, 1.0_dp, gs_coeffs, work_mat, 0.0_dp, eval_mat)
1795 :
1796 0 : CALL cp_fm_get_diag(eval_mat, diag)
1797 0 : donor_state%energy_evals(:, ispin) = diag(:)
1798 :
1799 : END DO
1800 :
1801 0 : DEALLOCATE (diag)
1802 : END IF
1803 :
1804 : ! Clean-up
1805 50 : CALL cp_fm_release(work_mat)
1806 50 : CALL cp_fm_release(eval_mat)
1807 150 : CALL cp_fm_struct_release(eval_mat_struct)
1808 :
1809 : END IF ! do_localize and/or ROKS
1810 :
1811 : ! Allocate and initialize GW2X corrected IPs as energy_evals
1812 320 : ALLOCATE (donor_state%gw2x_evals(SIZE(donor_state%energy_evals, 1), SIZE(donor_state%energy_evals, 2)))
1813 276 : donor_state%gw2x_evals(:, :) = donor_state%energy_evals(:, :)
1814 :
1815 : ! Clean-up
1816 80 : CALL cp_fm_struct_release(gs_struct)
1817 80 : DEALLOCATE (first_sgf)
1818 :
1819 80 : IF (output_unit > 0) WRITE (UNIT=output_unit, FMT="(T5,A)") " "
1820 :
1821 168 : DO ispin = 1, nspins
1822 168 : IF (output_unit > 0) THEN
1823 : WRITE (UNIT=output_unit, FMT="(T5,A,I1,A,F7.5,A,I4)") &
1824 44 : "The next best overlap for spin ", ispin, " is ", next_best_overlap(ispin), &
1825 88 : " for MO with index ", next_best_overlap_ind(ispin)
1826 : END IF
1827 : END DO
1828 80 : IF (output_unit > 0) WRITE (UNIT=output_unit, FMT="(T5,A)") " "
1829 :
1830 : ELSE
1831 0 : CPABORT("A core donor state could not be assigned MO(s). Increasing NSEARCH might help.")
1832 : END IF
1833 :
1834 320 : END SUBROUTINE assign_mos_to_donor_state
1835 :
1836 : ! **************************************************************************************************
1837 : !> \brief Compute the centers and spreads of (core) MOs using the Berry phase operator
1838 : !> \param xas_tdp_env ...
1839 : !> \param xas_tdp_control ...
1840 : !> \param qs_env ...
1841 : !> \note xas_tdp_env%qs_loc_env is used and modified. OK since no localization done after this
1842 : !> subroutine is used.
1843 : ! **************************************************************************************************
1844 92 : SUBROUTINE find_mo_centers(xas_tdp_env, xas_tdp_control, qs_env)
1845 :
1846 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1847 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1848 : TYPE(qs_environment_type), POINTER :: qs_env
1849 :
1850 : INTEGER :: dim_op, i, ispin, j, n_centers, nao, &
1851 : nspins
1852 : REAL(dp), DIMENSION(6) :: weights
1853 : TYPE(cell_type), POINTER :: cell
1854 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
1855 : TYPE(cp_fm_struct_type), POINTER :: tmp_fm_struct
1856 : TYPE(cp_fm_type) :: opvec
1857 92 : TYPE(cp_fm_type), ALLOCATABLE, DIMENSION(:, :) :: zij_fm_set
1858 92 : TYPE(cp_fm_type), DIMENSION(:), POINTER :: moloc_coeff
1859 : TYPE(cp_fm_type), POINTER :: vectors
1860 92 : TYPE(dbcsr_p_type), DIMENSION(:, :), POINTER :: op_sm_set
1861 : TYPE(mp_para_env_type), POINTER :: para_env
1862 : TYPE(qs_loc_env_type), POINTER :: qs_loc_env
1863 : TYPE(section_vals_type), POINTER :: print_loc_section, prog_run_info
1864 :
1865 92 : NULLIFY (qs_loc_env, cell, print_loc_section, op_sm_set, moloc_coeff, vectors)
1866 92 : NULLIFY (tmp_fm_struct, para_env, blacs_env, prog_run_info)
1867 :
1868 : ! Initialization
1869 92 : print_loc_section => xas_tdp_control%print_loc_subsection
1870 92 : n_centers = xas_tdp_control%n_search
1871 92 : CALL get_qs_env(qs_env=qs_env, para_env=para_env, blacs_env=blacs_env, cell=cell)
1872 :
1873 : ! Set print option to debug to keep clean output file
1874 92 : prog_run_info => section_vals_get_subs_vals(print_loc_section, "PROGRAM_RUN_INFO")
1875 : CALL section_vals_val_set(prog_run_info, keyword_name="_SECTION_PARAMETERS_", &
1876 92 : i_val=debug_print_level)
1877 :
1878 : ! Re-initialize the qs_loc_env to get the current MOs. Use force_loc because needed for centers
1879 92 : CALL reinit_qs_loc_env(xas_tdp_env%qs_loc_env, n_centers, xas_tdp_control%do_uks, qs_env)
1880 92 : qs_loc_env => xas_tdp_env%qs_loc_env
1881 :
1882 : ! Get what we need from the qs_lovc_env
1883 : CALL get_qs_loc_env(qs_loc_env=qs_loc_env, weights=weights, op_sm_set=op_sm_set, &
1884 92 : moloc_coeff=moloc_coeff)
1885 :
1886 : ! Prepare for zij
1887 92 : vectors => moloc_coeff(1)
1888 92 : CALL cp_fm_get_info(vectors, nrow_global=nao)
1889 92 : CALL cp_fm_create(opvec, vectors%matrix_struct)
1890 :
1891 : CALL cp_fm_struct_create(tmp_fm_struct, para_env=para_env, context=blacs_env, &
1892 92 : ncol_global=n_centers, nrow_global=n_centers)
1893 :
1894 92 : IF (cell%orthorhombic) THEN
1895 : dim_op = 3
1896 : ELSE
1897 0 : dim_op = 6
1898 : END IF
1899 1012 : ALLOCATE (zij_fm_set(2, dim_op))
1900 368 : DO i = 1, dim_op
1901 920 : DO j = 1, 2
1902 828 : CALL cp_fm_create(zij_fm_set(j, i), tmp_fm_struct)
1903 : END DO
1904 : END DO
1905 :
1906 : ! If spin-unrestricted, need to go spin by spin
1907 92 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
1908 :
1909 192 : DO ispin = 1, nspins
1910 : ! zij computation, copied from qs_loc_methods:optimize_loc_berry
1911 100 : vectors => moloc_coeff(ispin)
1912 400 : DO i = 1, dim_op
1913 1000 : DO j = 1, 2
1914 600 : CALL cp_fm_set_all(zij_fm_set(j, i), 0.0_dp)
1915 600 : CALL cp_dbcsr_sm_fm_multiply(op_sm_set(j, i)%matrix, vectors, opvec, ncol=n_centers)
1916 : CALL parallel_gemm("T", "N", n_centers, n_centers, nao, 1.0_dp, vectors, opvec, 0.0_dp, &
1917 900 : zij_fm_set(j, i))
1918 : END DO
1919 : END DO
1920 :
1921 : ! Compute centers (and spread)
1922 : CALL centers_spreads_berry(qs_loc_env=qs_loc_env, zij=zij_fm_set, nmoloc=n_centers, &
1923 : cell=cell, weights=weights, ispin=ispin, &
1924 192 : print_loc_section=print_loc_section, only_initial_out=.TRUE.)
1925 : END DO !ispins
1926 :
1927 : ! Clean-up
1928 92 : CALL cp_fm_release(opvec)
1929 92 : CALL cp_fm_struct_release(tmp_fm_struct)
1930 92 : CALL cp_fm_release(zij_fm_set)
1931 :
1932 : ! Make sure we leave with the correct do_loc value
1933 92 : qs_loc_env%do_localize = xas_tdp_control%do_loc
1934 :
1935 276 : END SUBROUTINE find_mo_centers
1936 :
1937 : ! **************************************************************************************************
1938 : !> \brief Prints the MO to donor_state assocaition with overlap and Mulliken population analysis
1939 : !> \param xas_tdp_env ...
1940 : !> \param xas_tdp_control ...
1941 : !> \param qs_env ...
1942 : !> \note Called only in case of CHECK_ONLY run
1943 : ! **************************************************************************************************
1944 0 : SUBROUTINE print_checks(xas_tdp_env, xas_tdp_control, qs_env)
1945 :
1946 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1947 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1948 : TYPE(qs_environment_type), POINTER :: qs_env
1949 :
1950 : CHARACTER(LEN=default_string_length) :: kind_name
1951 : INTEGER :: current_state_index, iat, iatom, ikind, &
1952 : istate, output_unit, tmp_index
1953 0 : INTEGER, DIMENSION(:), POINTER :: atoms_of_kind
1954 0 : TYPE(atomic_kind_type), DIMENSION(:), POINTER :: atomic_kind_set
1955 : TYPE(donor_state_type), POINTER :: current_state
1956 :
1957 0 : NULLIFY (atomic_kind_set, atoms_of_kind, current_state)
1958 :
1959 0 : output_unit = cp_logger_get_default_io_unit()
1960 :
1961 0 : IF (output_unit > 0) THEN
1962 : WRITE (output_unit, "(/,T3,A,/,T3,A,/,T3,A)") &
1963 0 : "# Check the donor states for their quality. They need to have a well defined type ", &
1964 0 : " (1s, 2s, etc) which is indicated by the overlap. They also need to be localized, ", &
1965 0 : " for which the Mulliken population analysis is one indicator (must be close to 1.0)"
1966 : END IF
1967 :
1968 : ! Loop over the donor states (as in the main xas_tdp loop)
1969 0 : CALL get_qs_env(qs_env=qs_env, atomic_kind_set=atomic_kind_set)
1970 0 : current_state_index = 1
1971 :
1972 : !loop over atomic kinds
1973 0 : DO ikind = 1, SIZE(atomic_kind_set)
1974 :
1975 : CALL get_atomic_kind(atomic_kind=atomic_kind_set(ikind), name=kind_name, &
1976 0 : atom_list=atoms_of_kind)
1977 :
1978 0 : IF (.NOT. ANY(xas_tdp_env%ex_kind_indices == ikind)) CYCLE
1979 :
1980 : !loop over atoms of kind
1981 0 : DO iat = 1, SIZE(atoms_of_kind)
1982 0 : iatom = atoms_of_kind(iat)
1983 :
1984 0 : IF (.NOT. ANY(xas_tdp_env%ex_atom_indices == iatom)) CYCLE
1985 0 : tmp_index = locate(xas_tdp_env%ex_atom_indices, iatom)
1986 :
1987 : !loop over states of excited atom
1988 0 : DO istate = 1, SIZE(xas_tdp_env%state_types, 1)
1989 :
1990 0 : IF (xas_tdp_env%state_types(istate, tmp_index) == xas_not_excited) CYCLE
1991 :
1992 0 : current_state => xas_tdp_env%donor_states(current_state_index)
1993 : CALL set_donor_state(current_state, at_index=iatom, &
1994 : at_symbol=kind_name, kind_index=ikind, &
1995 0 : state_type=xas_tdp_env%state_types(istate, tmp_index))
1996 :
1997 0 : IF (output_unit > 0) THEN
1998 : WRITE (output_unit, "(/,T4,A,A2,A,I4,A,A,A)") &
1999 0 : "-Donor state of type ", xas_tdp_env%state_type_char(current_state%state_type), &
2000 0 : " for atom", current_state%at_index, " of kind ", TRIM(current_state%at_symbol), ":"
2001 : END IF
2002 :
2003 : !Assign the MOs and perform Mulliken
2004 0 : CALL assign_mos_to_donor_state(current_state, xas_tdp_env, xas_tdp_control, qs_env)
2005 0 : CALL perform_mulliken_on_donor_state(current_state, qs_env)
2006 :
2007 0 : current_state_index = current_state_index + 1
2008 0 : NULLIFY (current_state)
2009 :
2010 : END DO !istate
2011 : END DO !iat
2012 : END DO !ikind
2013 :
2014 0 : IF (output_unit > 0) THEN
2015 : WRITE (output_unit, "(/,T5,A)") &
2016 0 : "Use LOCALIZE and/or increase N_SEARCH for better results, if so required."
2017 : END IF
2018 :
2019 0 : END SUBROUTINE print_checks
2020 :
2021 : ! **************************************************************************************************
2022 : !> \brief Computes the required multipole moment in the length representation for a given atom
2023 : !> \param iatom index of the given atom
2024 : !> \param xas_tdp_env ...
2025 : !> \param xas_tdp_control ...
2026 : !> \param qs_env ...
2027 : !> \note Assumes that wither dipole or quadrupole in length rep is required
2028 : ! **************************************************************************************************
2029 24 : SUBROUTINE compute_lenrep_multipole(iatom, xas_tdp_env, xas_tdp_control, qs_env)
2030 :
2031 : INTEGER, INTENT(IN) :: iatom
2032 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2033 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2034 : TYPE(qs_environment_type), POINTER :: qs_env
2035 :
2036 : INTEGER :: i, order
2037 : REAL(dp), DIMENSION(3) :: rc
2038 24 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: work
2039 24 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
2040 :
2041 24 : NULLIFY (work, particle_set)
2042 :
2043 24 : CALL get_qs_env(qs_env, particle_set=particle_set)
2044 96 : rc = particle_set(iatom)%r
2045 :
2046 240 : ALLOCATE (work(9))
2047 24 : IF (xas_tdp_control%dipole_form == xas_dip_len) THEN
2048 96 : DO i = 1, 3
2049 72 : CALL dbcsr_set(xas_tdp_env%dipmat(i)%matrix, 0.0_dp)
2050 96 : work(i)%matrix => xas_tdp_env%dipmat(i)%matrix
2051 : END DO
2052 24 : order = 1
2053 : END IF
2054 24 : IF (xas_tdp_control%do_quad) THEN
2055 0 : DO i = 1, 6
2056 0 : CALL dbcsr_set(xas_tdp_env%quadmat(i)%matrix, 0.0_dp)
2057 0 : work(3 + i)%matrix => xas_tdp_env%quadmat(i)%matrix
2058 : END DO
2059 0 : order = 2
2060 0 : IF (xas_tdp_control%dipole_form == xas_dip_vel) order = -2
2061 : END IF
2062 :
2063 : !enforce minimum image to avoid PBCs related issues, ok because localized densities
2064 24 : CALL rRc_xyz_ao(work, qs_env, rc, order=order, minimum_image=.TRUE.)
2065 24 : DEALLOCATE (work)
2066 :
2067 24 : END SUBROUTINE compute_lenrep_multipole
2068 :
2069 : ! **************************************************************************************************
2070 : !> \brief Computes the oscillator strength based on the dipole moment (velocity or length rep) for
2071 : !> all available excitation energies and store the results in the donor_state. There is no
2072 : !> triplet dipole in the spin-restricted ground state.
2073 : !> \param donor_state the donor state which is excited
2074 : !> \param xas_tdp_control ...
2075 : !> \param xas_tdp_env ...
2076 : !> \note The oscillator strength is a scalar: osc_str = 2/(3*omega)*(dipole_v)^2 in the velocity rep
2077 : !> or : osc_str = 2/3*omega*(dipole_r)^2 in the length representation
2078 : !> The formulae for the dipoles come from the trace of the dipole operator with the transition
2079 : !> densities, i.e. what we get from solving the xas_tdp problem. Same procedure with or wo TDA
2080 : ! **************************************************************************************************
2081 68 : SUBROUTINE compute_dipole_fosc(donor_state, xas_tdp_control, xas_tdp_env)
2082 :
2083 : TYPE(donor_state_type), POINTER :: donor_state
2084 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2085 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2086 :
2087 : CHARACTER(len=*), PARAMETER :: routineN = 'compute_dipole_fosc'
2088 :
2089 : INTEGER :: handle, iosc, j, nao, ndo_mo, ndo_so, &
2090 : ngs, nosc, nspins
2091 : LOGICAL :: do_sc, do_sg
2092 : REAL(dp) :: alpha_xyz, beta_xyz, osc_xyz, pref
2093 68 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: alpha_contr, beta_contr, tot_contr
2094 68 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: dip_block
2095 68 : REAL(dp), DIMENSION(:), POINTER :: lr_evals
2096 68 : REAL(dp), DIMENSION(:, :), POINTER :: alpha_osc, beta_osc, osc_str
2097 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2098 : TYPE(cp_fm_struct_type), POINTER :: col_struct, mat_struct
2099 : TYPE(cp_fm_type) :: col_work, mat_work
2100 : TYPE(cp_fm_type), POINTER :: lr_coeffs
2101 68 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: dipmat
2102 : TYPE(mp_para_env_type), POINTER :: para_env
2103 :
2104 68 : NULLIFY (dipmat, col_struct, mat_struct, para_env, blacs_env, lr_coeffs)
2105 68 : NULLIFY (lr_evals, osc_str, alpha_osc, beta_osc)
2106 :
2107 68 : CALL timeset(routineN, handle)
2108 :
2109 : ! Initialization
2110 68 : do_sc = xas_tdp_control%do_spin_cons
2111 68 : do_sg = xas_tdp_control%do_singlet
2112 68 : IF (do_sc) THEN
2113 8 : nspins = 2
2114 8 : lr_evals => donor_state%sc_evals
2115 8 : lr_coeffs => donor_state%sc_coeffs
2116 60 : ELSE IF (do_sg) THEN
2117 60 : nspins = 1
2118 60 : lr_evals => donor_state%sg_evals
2119 60 : lr_coeffs => donor_state%sg_coeffs
2120 : ELSE
2121 0 : CPABORT("Dipole oscilaltor strength only for singlets and spin-conserving excitations.")
2122 : END IF
2123 68 : ndo_mo = donor_state%ndo_mo
2124 68 : ndo_so = ndo_mo*nspins
2125 68 : ngs = ndo_so; IF (xas_tdp_control%do_roks) ngs = ndo_mo !in ROKS, same gs coeffs
2126 68 : nosc = SIZE(lr_evals)
2127 340 : ALLOCATE (donor_state%osc_str(nosc, 4), donor_state%alpha_osc(nosc, 4), donor_state%beta_osc(nosc, 4))
2128 68 : osc_str => donor_state%osc_str
2129 68 : alpha_osc => donor_state%alpha_osc
2130 68 : beta_osc => donor_state%beta_osc
2131 4436 : osc_str = 0.0_dp
2132 4436 : alpha_osc = 0.0_dp
2133 4436 : beta_osc = 0.0_dp
2134 68 : dipmat => xas_tdp_env%dipmat
2135 :
2136 : ! do some work matrix initialization
2137 : CALL cp_fm_get_info(donor_state%gs_coeffs, matrix_struct=col_struct, para_env=para_env, &
2138 68 : context=blacs_env, nrow_global=nao)
2139 : CALL cp_fm_struct_create(mat_struct, para_env=para_env, context=blacs_env, &
2140 68 : nrow_global=ndo_so*nosc, ncol_global=ngs)
2141 68 : CALL cp_fm_create(mat_work, mat_struct)
2142 68 : CALL cp_fm_create(col_work, col_struct)
2143 :
2144 544 : ALLOCATE (tot_contr(ndo_mo), dip_block(ndo_so, ngs), alpha_contr(ndo_mo), beta_contr(ndo_mo))
2145 68 : pref = 2.0_dp; IF (do_sc) pref = 1.0_dp !because of singlet definition u = 1/sqrt(2)(c_a+c_b)
2146 :
2147 : ! Looping over cartesian coord
2148 272 : DO j = 1, 3
2149 :
2150 : !Compute dip*gs_coeffs
2151 204 : CALL cp_dbcsr_sm_fm_multiply(dipmat(j)%matrix, donor_state%gs_coeffs, col_work, ncol=ngs)
2152 : !compute lr_coeffs*dip*gs_coeffs
2153 204 : CALL parallel_gemm('T', 'N', ndo_so*nosc, ngs, nao, 1.0_dp, lr_coeffs, col_work, 0.0_dp, mat_work)
2154 :
2155 : !Loop over the excited states
2156 3344 : DO iosc = 1, nosc
2157 :
2158 6432 : tot_contr = 0.0_dp
2159 : CALL cp_fm_get_submatrix(fm=mat_work, target_m=dip_block, start_row=(iosc - 1)*ndo_so + 1, &
2160 3072 : start_col=1, n_rows=ndo_so, n_cols=ngs)
2161 3072 : IF (do_sg) THEN
2162 2448 : tot_contr(:) = get_diag(dip_block)
2163 624 : ELSE IF (do_sc .AND. xas_tdp_control%do_uks) THEN
2164 624 : alpha_contr(:) = get_diag(dip_block(1:ndo_mo, 1:ndo_mo))
2165 624 : beta_contr(:) = get_diag(dip_block(ndo_mo + 1:ndo_so, ndo_mo + 1:ndo_so))
2166 1392 : tot_contr(:) = alpha_contr(:) + beta_contr(:)
2167 : ELSE
2168 : !roks
2169 0 : alpha_contr(:) = get_diag(dip_block(1:ndo_mo, :))
2170 0 : beta_contr(:) = get_diag(dip_block(ndo_mo + 1:ndo_so, :))
2171 0 : tot_contr(:) = alpha_contr(:) + beta_contr(:)
2172 : END IF
2173 :
2174 6432 : osc_xyz = SUM(tot_contr)**2
2175 6432 : alpha_xyz = SUM(alpha_contr)**2
2176 6432 : beta_xyz = SUM(beta_contr)**2
2177 :
2178 3072 : alpha_osc(iosc, 4) = alpha_osc(iosc, 4) + alpha_xyz
2179 3072 : alpha_osc(iosc, j) = alpha_xyz
2180 :
2181 3072 : beta_osc(iosc, 4) = beta_osc(iosc, 4) + beta_xyz
2182 3072 : beta_osc(iosc, j) = beta_xyz
2183 :
2184 3072 : osc_str(iosc, 4) = osc_str(iosc, 4) + osc_xyz
2185 3276 : osc_str(iosc, j) = osc_xyz
2186 :
2187 : END DO !iosc
2188 : END DO !j
2189 :
2190 : !compute the prefactor
2191 340 : DO j = 1, 4
2192 340 : IF (xas_tdp_control%dipole_form == xas_dip_len) THEN
2193 3248 : osc_str(:, j) = pref*2.0_dp/3.0_dp*lr_evals(:)*osc_str(:, j)
2194 3248 : alpha_osc(:, j) = pref*2.0_dp/3.0_dp*lr_evals(:)*alpha_osc(:, j)
2195 3248 : beta_osc(:, j) = pref*2.0_dp/3.0_dp*lr_evals(:)*beta_osc(:, j)
2196 : ELSE
2197 5488 : osc_str(:, j) = pref*2.0_dp/3.0_dp/lr_evals(:)*osc_str(:, j)
2198 5488 : alpha_osc(:, j) = pref*2.0_dp/3.0_dp/lr_evals(:)*alpha_osc(:, j)
2199 5488 : beta_osc(:, j) = pref*2.0_dp/3.0_dp/lr_evals(:)*beta_osc(:, j)
2200 : END IF
2201 : END DO
2202 :
2203 : !clean-up
2204 68 : CALL cp_fm_release(mat_work)
2205 68 : CALL cp_fm_release(col_work)
2206 68 : CALL cp_fm_struct_release(mat_struct)
2207 :
2208 68 : CALL timestop(handle)
2209 :
2210 272 : END SUBROUTINE compute_dipole_fosc
2211 :
2212 : ! **************************************************************************************************
2213 : !> \brief Computes the oscillator strength due to the electric quadrupole moment and store it in
2214 : !> the donor_state (for singlet or spin-conserving)
2215 : !> \param donor_state the donor state which is excited
2216 : !> \param xas_tdp_control ...
2217 : !> \param xas_tdp_env ...
2218 : !> \note Formula: 1/20*a_fine^2*omega^3 * sum_ab (sum_i r_ia*r_ib - 1/3*ri^2*delta_ab)
2219 : ! **************************************************************************************************
2220 0 : SUBROUTINE compute_quadrupole_fosc(donor_state, xas_tdp_control, xas_tdp_env)
2221 :
2222 : TYPE(donor_state_type), POINTER :: donor_state
2223 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2224 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2225 :
2226 : CHARACTER(len=*), PARAMETER :: routineN = 'compute_quadrupole_fosc'
2227 :
2228 : INTEGER :: handle, iosc, j, nao, ndo_mo, ndo_so, &
2229 : ngs, nosc, nspins
2230 : LOGICAL :: do_sc, do_sg
2231 : REAL(dp) :: pref
2232 0 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: tot_contr, trace
2233 0 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: quad_block
2234 0 : REAL(dp), DIMENSION(:), POINTER :: lr_evals, osc_str
2235 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2236 : TYPE(cp_fm_struct_type), POINTER :: col_struct, mat_struct
2237 : TYPE(cp_fm_type) :: col_work, mat_work
2238 : TYPE(cp_fm_type), POINTER :: lr_coeffs
2239 0 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: quadmat
2240 : TYPE(mp_para_env_type), POINTER :: para_env
2241 :
2242 0 : NULLIFY (lr_evals, osc_str, lr_coeffs, col_struct, mat_struct, para_env)
2243 0 : NULLIFY (blacs_env)
2244 :
2245 0 : CALL timeset(routineN, handle)
2246 :
2247 : ! Initialization
2248 0 : do_sc = xas_tdp_control%do_spin_cons
2249 0 : do_sg = xas_tdp_control%do_singlet
2250 0 : IF (do_sc) THEN
2251 0 : nspins = 2
2252 0 : lr_evals => donor_state%sc_evals
2253 0 : lr_coeffs => donor_state%sc_coeffs
2254 0 : ELSE IF (do_sg) THEN
2255 0 : nspins = 1
2256 0 : lr_evals => donor_state%sg_evals
2257 0 : lr_coeffs => donor_state%sg_coeffs
2258 : ELSE
2259 0 : CPABORT("Quadrupole oscillator strengths only for singlet and spin-conserving excitations")
2260 : END IF
2261 0 : ndo_mo = donor_state%ndo_mo
2262 0 : ndo_so = ndo_mo*nspins
2263 0 : ngs = ndo_so; IF (xas_tdp_control%do_roks) ngs = ndo_mo !only alpha do_mo in ROKS
2264 0 : nosc = SIZE(lr_evals)
2265 0 : ALLOCATE (donor_state%quad_osc_str(nosc))
2266 0 : osc_str => donor_state%quad_osc_str
2267 0 : osc_str = 0.0_dp
2268 0 : quadmat => xas_tdp_env%quadmat
2269 :
2270 : !work matrices init
2271 : CALL cp_fm_get_info(donor_state%gs_coeffs, matrix_struct=col_struct, para_env=para_env, &
2272 0 : context=blacs_env, nrow_global=nao)
2273 : CALL cp_fm_struct_create(mat_struct, para_env=para_env, context=blacs_env, &
2274 0 : nrow_global=ndo_so*nosc, ncol_global=ngs)
2275 0 : CALL cp_fm_create(mat_work, mat_struct)
2276 0 : CALL cp_fm_create(col_work, col_struct)
2277 :
2278 0 : ALLOCATE (quad_block(ndo_so, ngs), tot_contr(ndo_mo))
2279 0 : pref = 2.0_dp; IF (do_sc) pref = 1.0_dp !because of singlet definition u = 1/sqrt(2)*...
2280 0 : ALLOCATE (trace(nosc))
2281 0 : trace = 0.0_dp
2282 :
2283 : !Loop over the cartesioan coord :x2, xy, xz, y2, yz, z2
2284 0 : DO j = 1, 6
2285 :
2286 : !Compute quad*gs_coeffs
2287 0 : CALL cp_dbcsr_sm_fm_multiply(quadmat(j)%matrix, donor_state%gs_coeffs, col_work, ncol=ngs)
2288 : !compute lr_coeffs*quadmat*gs_coeffs
2289 0 : CALL parallel_gemm('T', 'N', ndo_so*nosc, ngs, nao, 1.0_dp, lr_coeffs, col_work, 0.0_dp, mat_work)
2290 :
2291 : !Loop over the excited states
2292 0 : DO iosc = 1, nosc
2293 :
2294 0 : tot_contr = 0.0_dp
2295 : CALL cp_fm_get_submatrix(fm=mat_work, target_m=quad_block, start_row=(iosc - 1)*ndo_so + 1, &
2296 0 : start_col=1, n_rows=ndo_so, n_cols=ngs)
2297 :
2298 0 : IF (do_sg) THEN
2299 0 : tot_contr(:) = get_diag(quad_block)
2300 0 : ELSE IF (do_sc .AND. xas_tdp_control%do_uks) THEN
2301 0 : tot_contr(:) = get_diag(quad_block(1:ndo_mo, 1:ndo_mo)) !alpha
2302 0 : tot_contr(:) = tot_contr(:) + get_diag(quad_block(ndo_mo + 1:ndo_so, ndo_mo + 1:ndo_so)) !beta
2303 : ELSE
2304 : !roks
2305 0 : tot_contr(:) = get_diag(quad_block(1:ndo_mo, :)) !alpha
2306 0 : tot_contr(:) = tot_contr(:) + get_diag(quad_block(ndo_mo + 1:ndo_so, :)) !beta
2307 : END IF
2308 :
2309 : !if x2, y2, or z2 direction, need to update the trace (for later)
2310 0 : IF (j == 1 .OR. j == 4 .OR. j == 6) THEN
2311 0 : osc_str(iosc) = osc_str(iosc) + SUM(tot_contr)**2
2312 0 : trace(iosc) = trace(iosc) + SUM(tot_contr)
2313 :
2314 : !if xy, xz or yz, need to count twice the contribution (for yx, zx and zy)
2315 : ELSE
2316 0 : osc_str(iosc) = osc_str(iosc) + 2.0_dp*SUM(tot_contr)**2
2317 : END IF
2318 :
2319 : END DO !iosc
2320 : END DO !j
2321 :
2322 : !compute the prefactor, and remove 1/3*trace^2
2323 0 : osc_str(:) = pref*1._dp/20._dp*a_fine**2*lr_evals(:)**3*(osc_str(:) - 1._dp/3._dp*trace(:)**2)
2324 :
2325 : !clean-up
2326 0 : CALL cp_fm_release(mat_work)
2327 0 : CALL cp_fm_release(col_work)
2328 0 : CALL cp_fm_struct_release(mat_struct)
2329 :
2330 0 : CALL timestop(handle)
2331 :
2332 0 : END SUBROUTINE compute_quadrupole_fosc
2333 :
2334 : ! **************************************************************************************************
2335 : !> \brief Writes the core MOs to excited atoms associations in the main output file
2336 : !> \param xas_tdp_env ...
2337 : !> \param xas_tdp_control ...
2338 : !> \param qs_env ...
2339 : !> \note Look at alpha spin MOs, as we are dealing with core states and alpha/beta MOs are the same
2340 : ! **************************************************************************************************
2341 58 : SUBROUTINE write_mos_to_ex_atoms_association(xas_tdp_env, xas_tdp_control, qs_env)
2342 :
2343 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2344 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2345 : TYPE(qs_environment_type), POINTER :: qs_env
2346 :
2347 : CHARACTER(LEN=default_string_length) :: kind_name
2348 : INTEGER :: at_index, imo, ispin, nmo, nspins, &
2349 : output_unit, tmp_index
2350 : INTEGER, DIMENSION(3) :: perd_init
2351 58 : INTEGER, DIMENSION(:), POINTER :: ex_atom_indices
2352 58 : INTEGER, DIMENSION(:, :, :), POINTER :: mos_of_ex_atoms
2353 : REAL(dp) :: dist, mo_spread
2354 : REAL(dp), DIMENSION(3) :: at_pos, r_ac, wfn_center
2355 : TYPE(cell_type), POINTER :: cell
2356 58 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
2357 :
2358 58 : NULLIFY (cell, particle_set, mos_of_ex_atoms, ex_atom_indices)
2359 :
2360 116 : output_unit = cp_logger_get_default_io_unit()
2361 :
2362 58 : IF (output_unit > 0) THEN
2363 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/,T3,A,/,T3,A)") &
2364 29 : " Associated Associated Distance to MO spread (Ang^2)", &
2365 29 : "Spin MO index atom index atom kind MO center (Ang) -w_i ln(|z_ij|^2)", &
2366 58 : "---------------------------------------------------------------------------------"
2367 : END IF
2368 :
2369 : ! Initialization
2370 58 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
2371 58 : mos_of_ex_atoms => xas_tdp_env%mos_of_ex_atoms
2372 58 : ex_atom_indices => xas_tdp_env%ex_atom_indices
2373 58 : nmo = xas_tdp_control%n_search
2374 58 : CALL get_qs_env(qs_env=qs_env, particle_set=particle_set, cell=cell)
2375 :
2376 : ! because the use of Berry's phase operator implies PBCs
2377 232 : perd_init = cell%perd
2378 232 : cell%perd = 1
2379 :
2380 : ! Retrieving all the info for each MO and spin
2381 334 : DO imo = 1, nmo
2382 626 : DO ispin = 1, nspins
2383 :
2384 : ! each Mo is associated to at most one atom (only 1 in array of -1)
2385 800 : IF (ANY(mos_of_ex_atoms(imo, :, ispin) == 1)) THEN
2386 296 : tmp_index = MAXLOC(mos_of_ex_atoms(imo, :, ispin), 1)
2387 134 : at_index = ex_atom_indices(tmp_index)
2388 134 : kind_name = particle_set(at_index)%atomic_kind%name
2389 :
2390 536 : at_pos = particle_set(at_index)%r
2391 536 : wfn_center = xas_tdp_env%qs_loc_env%localized_wfn_control%centers_set(ispin)%array(1:3, imo)
2392 134 : r_ac = pbc(at_pos, wfn_center, cell)
2393 536 : dist = NORM2(r_ac)
2394 : ! convert distance from a.u. to Angstrom
2395 134 : dist = dist*angstrom
2396 :
2397 134 : mo_spread = xas_tdp_env%qs_loc_env%localized_wfn_control%centers_set(ispin)%array(4, imo)
2398 134 : mo_spread = mo_spread*angstrom*angstrom
2399 :
2400 134 : IF (output_unit > 0) THEN
2401 : WRITE (UNIT=output_unit, FMT="(T3,I4,I10,I14,A14,ES19.3,ES20.3)") &
2402 67 : ispin, imo, at_index, TRIM(kind_name), dist, mo_spread
2403 : END IF
2404 :
2405 : END IF
2406 : END DO !ispin
2407 : END DO !imo
2408 :
2409 58 : IF (output_unit > 0) THEN
2410 : WRITE (UNIT=output_unit, FMT="(T3,A,/)") &
2411 29 : "---------------------------------------------------------------------------------"
2412 : END IF
2413 :
2414 : ! Go back to initial BCs
2415 232 : cell%perd = perd_init
2416 :
2417 58 : END SUBROUTINE write_mos_to_ex_atoms_association
2418 :
2419 : ! **************************************************************************************************
2420 : !> \brief Performs Mulliken population analysis for the MO(s) of a donor_state_type so that user
2421 : !> can verify it is indeed a core state
2422 : !> \param donor_state ...
2423 : !> \param qs_env ...
2424 : !> \note This is a specific case of Mulliken analysis. In general one computes sum_i (SP)_ii, where
2425 : !> i labels the basis function centered on the atom of interest. For a specific MO with index
2426 : !> j, one need to compute sum_{ik} c_{ij} S_{ik} c_{kj}, k = 1,nao
2427 : ! **************************************************************************************************
2428 80 : SUBROUTINE perform_mulliken_on_donor_state(donor_state, qs_env)
2429 : TYPE(donor_state_type), POINTER :: donor_state
2430 : TYPE(qs_environment_type), POINTER :: qs_env
2431 :
2432 : INTEGER :: at_index, i, ispin, nao, natom, ndo_mo, &
2433 : ndo_so, nsgf, nspins, output_unit
2434 80 : INTEGER, DIMENSION(:), POINTER :: first_sgf, last_sgf
2435 80 : INTEGER, DIMENSION(:, :), POINTER :: mo_indices
2436 80 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: mul_pop, pop_mat
2437 80 : REAL(dp), DIMENSION(:, :), POINTER :: work_array
2438 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2439 : TYPE(cp_fm_struct_type), POINTER :: col_vect_struct
2440 : TYPE(cp_fm_type) :: work_vect
2441 : TYPE(cp_fm_type), POINTER :: gs_coeffs
2442 80 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_s
2443 : TYPE(mp_para_env_type), POINTER :: para_env
2444 80 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
2445 80 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
2446 :
2447 80 : NULLIFY (mo_indices, qs_kind_set, particle_set, first_sgf, work_array)
2448 80 : NULLIFY (matrix_s, para_env, blacs_env, col_vect_struct, last_sgf)
2449 :
2450 : ! Initialization
2451 80 : at_index = donor_state%at_index
2452 80 : mo_indices => donor_state%mo_indices
2453 80 : ndo_mo = donor_state%ndo_mo
2454 80 : gs_coeffs => donor_state%gs_coeffs
2455 160 : output_unit = cp_logger_get_default_io_unit()
2456 80 : nspins = 1; IF (SIZE(mo_indices, 2) == 2) nspins = 2
2457 80 : ndo_so = ndo_mo*nspins
2458 320 : ALLOCATE (mul_pop(ndo_mo, nspins))
2459 276 : mul_pop = 0.0_dp
2460 :
2461 : CALL get_qs_env(qs_env=qs_env, particle_set=particle_set, qs_kind_set=qs_kind_set, &
2462 80 : para_env=para_env, blacs_env=blacs_env, matrix_s=matrix_s)
2463 80 : CALL cp_fm_get_info(gs_coeffs, nrow_global=nao, matrix_struct=col_vect_struct)
2464 :
2465 80 : natom = SIZE(particle_set, 1)
2466 240 : ALLOCATE (first_sgf(natom))
2467 160 : ALLOCATE (last_sgf(natom))
2468 :
2469 80 : CALL get_particle_set(particle_set, qs_kind_set, first_sgf=first_sgf, last_sgf=last_sgf)
2470 80 : nsgf = last_sgf(at_index) - first_sgf(at_index) + 1
2471 :
2472 80 : CALL cp_fm_create(work_vect, col_vect_struct)
2473 :
2474 : ! Take the product of S*coeffs
2475 80 : CALL cp_dbcsr_sm_fm_multiply(matrix_s(1)%matrix, gs_coeffs, work_vect, ncol=ndo_so)
2476 :
2477 : ! Only consider the product coeffs^T * S * coeffs on the atom of interest
2478 320 : ALLOCATE (work_array(nsgf, ndo_so))
2479 320 : ALLOCATE (pop_mat(ndo_so, ndo_so))
2480 :
2481 : CALL cp_fm_get_submatrix(fm=work_vect, target_m=work_array, start_row=first_sgf(at_index), &
2482 80 : start_col=1, n_rows=nsgf, n_cols=ndo_so, transpose=.FALSE.)
2483 :
2484 : CALL dgemm('T', 'N', ndo_so, ndo_so, nsgf, 1.0_dp, donor_state%contract_coeffs, nsgf, &
2485 80 : work_array, nsgf, 0.0_dp, pop_mat, ndo_so)
2486 :
2487 : ! The Mullikan population for the MOs in on the diagonal.
2488 168 : DO ispin = 1, nspins
2489 276 : DO i = 1, ndo_mo
2490 196 : mul_pop(i, ispin) = pop_mat((ispin - 1)*ndo_mo + i, (ispin - 1)*ndo_mo + i)
2491 : END DO
2492 : END DO
2493 :
2494 : ! Printing in main output file
2495 80 : IF (output_unit > 0) THEN
2496 : WRITE (UNIT=output_unit, FMT="(T5,A,/,T5,A)") &
2497 40 : "Mulliken population analysis retricted to the associated MO(s) yields: ", &
2498 80 : " Spin MO index charge"
2499 84 : DO ispin = 1, nspins
2500 138 : DO i = 1, ndo_mo
2501 : WRITE (UNIT=output_unit, FMT="(T51,I4,I10,F11.3)") &
2502 98 : ispin, mo_indices(i, ispin), mul_pop(i, ispin)
2503 : END DO
2504 : END DO
2505 : END IF
2506 :
2507 : ! Clean-up
2508 80 : DEALLOCATE (first_sgf, last_sgf, work_array)
2509 80 : CALL cp_fm_release(work_vect)
2510 :
2511 320 : END SUBROUTINE perform_mulliken_on_donor_state
2512 :
2513 : ! **************************************************************************************************
2514 : !> \brief write the PDOS wrt the LR-orbitals for the current donor_state and/or the CUBES files
2515 : !> \param ex_type the excitation type: singlet, triplet, spin-conserving, etc
2516 : !> \param donor_state ...
2517 : !> \param xas_tdp_env ...
2518 : !> \param xas_tdp_section ...
2519 : !> \param qs_env ...
2520 : ! **************************************************************************************************
2521 86 : SUBROUTINE xas_tdp_post(ex_type, donor_state, xas_tdp_env, xas_tdp_section, qs_env)
2522 :
2523 : INTEGER, INTENT(IN) :: ex_type
2524 : TYPE(donor_state_type), POINTER :: donor_state
2525 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2526 : TYPE(section_vals_type), POINTER :: xas_tdp_section
2527 : TYPE(qs_environment_type), POINTER :: qs_env
2528 :
2529 : CHARACTER(len=*), PARAMETER :: routineN = 'xas_tdp_post'
2530 :
2531 : CHARACTER(len=default_string_length) :: domo, domon, excite, pos, xas_mittle
2532 : INTEGER :: ex_state_idx, handle, ic, ido_mo, imo, irep, ispin, n_dependent, n_rep, nao, &
2533 : ncubes, ndo_mo, ndo_so, nlumo, nmo, nspins, output_unit
2534 74 : INTEGER, DIMENSION(:), POINTER :: bounds, list, state_list
2535 : LOGICAL :: append_cube, do_cubes, do_pdos, &
2536 : do_wfn_restart
2537 74 : REAL(dp), DIMENSION(:), POINTER :: lr_evals
2538 74 : REAL(dp), DIMENSION(:, :), POINTER :: centers
2539 74 : TYPE(atomic_kind_type), DIMENSION(:), POINTER :: atomic_kind_set
2540 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2541 : TYPE(cp_fm_struct_type), POINTER :: fm_struct, mo_struct
2542 : TYPE(cp_fm_type) :: mo_coeff, work_fm
2543 : TYPE(cp_fm_type), POINTER :: lr_coeffs
2544 : TYPE(cp_logger_type), POINTER :: logger
2545 74 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_s
2546 74 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
2547 : TYPE(mo_set_type), POINTER :: mo_set
2548 : TYPE(mp_para_env_type), POINTER :: para_env
2549 74 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
2550 74 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
2551 : TYPE(section_vals_type), POINTER :: print_key
2552 :
2553 74 : NULLIFY (atomic_kind_set, particle_set, qs_kind_set, mo_set, lr_evals, lr_coeffs)
2554 74 : NULLIFY (mo_struct, para_env, blacs_env, fm_struct, matrix_s, print_key, logger)
2555 74 : NULLIFY (bounds, state_list, list, mos)
2556 :
2557 : !Tests on what to do
2558 148 : logger => cp_get_default_logger()
2559 74 : do_pdos = .FALSE.; do_cubes = .FALSE.; do_wfn_restart = .FALSE.
2560 :
2561 74 : IF (BTEST(cp_print_key_should_output(logger%iter_info, xas_tdp_section, &
2562 2 : "PRINT%PDOS"), cp_p_file)) do_pdos = .TRUE.
2563 :
2564 74 : IF (BTEST(cp_print_key_should_output(logger%iter_info, xas_tdp_section, &
2565 2 : "PRINT%CUBES"), cp_p_file)) do_cubes = .TRUE.
2566 :
2567 74 : IF (BTEST(cp_print_key_should_output(logger%iter_info, xas_tdp_section, &
2568 2 : "PRINT%RESTART_WFN"), cp_p_file)) do_wfn_restart = .TRUE.
2569 :
2570 74 : IF (.NOT. (do_pdos .OR. do_cubes .OR. do_wfn_restart)) RETURN
2571 :
2572 4 : CALL timeset(routineN, handle)
2573 :
2574 : !Initialization
2575 : CALL get_qs_env(qs_env, atomic_kind_set=atomic_kind_set, particle_set=particle_set, &
2576 : qs_kind_set=qs_kind_set, para_env=para_env, blacs_env=blacs_env, &
2577 4 : matrix_s=matrix_s, mos=mos)
2578 :
2579 4 : SELECT CASE (ex_type)
2580 : CASE (tddfpt_spin_cons)
2581 0 : lr_evals => donor_state%sc_evals
2582 0 : lr_coeffs => donor_state%sc_coeffs
2583 0 : nspins = 2
2584 0 : excite = "spincons"
2585 : CASE (tddfpt_spin_flip)
2586 0 : lr_evals => donor_state%sf_evals
2587 0 : lr_coeffs => donor_state%sf_coeffs
2588 0 : nspins = 2
2589 0 : excite = "spinflip"
2590 : CASE (tddfpt_singlet)
2591 4 : lr_evals => donor_state%sg_evals
2592 4 : lr_coeffs => donor_state%sg_coeffs
2593 4 : nspins = 1
2594 4 : excite = "singlet"
2595 : CASE (tddfpt_triplet)
2596 0 : lr_evals => donor_state%tp_evals
2597 0 : lr_coeffs => donor_state%tp_coeffs
2598 0 : nspins = 1
2599 4 : excite = "triplet"
2600 : END SELECT
2601 :
2602 8 : SELECT CASE (donor_state%state_type)
2603 : CASE (xas_1s_type)
2604 4 : domo = "1s"
2605 : CASE (xas_2s_type)
2606 0 : domo = "2s"
2607 : CASE (xas_2p_type)
2608 4 : domo = "2p"
2609 : END SELECT
2610 :
2611 4 : ndo_mo = donor_state%ndo_mo
2612 4 : ndo_so = ndo_mo*nspins
2613 4 : nmo = SIZE(lr_evals)
2614 4 : CALL dbcsr_get_info(matrix_s(1)%matrix, nfullrows_total=nao)
2615 :
2616 : CALL cp_fm_struct_create(mo_struct, context=blacs_env, para_env=para_env, &
2617 4 : nrow_global=nao, ncol_global=nmo)
2618 4 : CALL cp_fm_create(mo_coeff, mo_struct)
2619 :
2620 : !Dump the TDDFT excited state AMEW wavefunction into a file for restart in RTP
2621 4 : IF (do_wfn_restart) THEN
2622 2 : BLOCK
2623 6 : TYPE(mo_set_type), DIMENSION(2) :: restart_mos
2624 2 : IF (.NOT. (nspins == 1 .AND. donor_state%state_type == xas_1s_type)) THEN
2625 0 : CPABORT("RESTART.wfn file only available for RKS K-edge XAS spectroscopy")
2626 : END IF
2627 :
2628 2 : CALL section_vals_val_get(xas_tdp_section, "PRINT%RESTART_WFN%EXCITED_STATE_INDEX", n_rep_val=n_rep)
2629 :
2630 4 : DO irep = 1, n_rep
2631 : CALL section_vals_val_get(xas_tdp_section, "PRINT%RESTART_WFN%EXCITED_STATE_INDEX", &
2632 2 : i_rep_val=irep, i_val=ex_state_idx)
2633 2 : CPASSERT(ex_state_idx <= SIZE(lr_evals))
2634 :
2635 6 : DO ispin = 1, 2
2636 4 : CALL duplicate_mo_set(restart_mos(ispin), mos(1))
2637 : ! Set the new occupation number in the case of spin-independent based calculaltion since the restart is spin-depedent
2638 4 : IF (SIZE(mos) == 1) &
2639 26 : restart_mos(ispin)%occupation_numbers = mos(1)%occupation_numbers/2
2640 : END DO
2641 :
2642 : CALL cp_fm_to_fm_submat(msource=lr_coeffs, mtarget=restart_mos(1)%mo_coeff, nrow=nao, &
2643 : ncol=1, s_firstrow=1, s_firstcol=ex_state_idx, t_firstrow=1, &
2644 2 : t_firstcol=donor_state%mo_indices(1, 1))
2645 :
2646 : xas_mittle = 'xasat'//TRIM(ADJUSTL(cp_to_string(donor_state%at_index)))//'_'//TRIM(domo)// &
2647 2 : '_'//TRIM(excite)//'_idx'//TRIM(ADJUSTL(cp_to_string(ex_state_idx)))
2648 : output_unit = cp_print_key_unit_nr(logger, xas_tdp_section, "PRINT%RESTART_WFN", &
2649 : extension=".wfn", file_status="REPLACE", &
2650 : file_action="WRITE", file_form="UNFORMATTED", &
2651 2 : middle_name=xas_mittle)
2652 :
2653 : CALL write_mo_set_low(restart_mos, particle_set=particle_set, &
2654 2 : qs_kind_set=qs_kind_set, ires=output_unit)
2655 :
2656 2 : CALL cp_print_key_finished_output(output_unit, logger, xas_tdp_section, "PRINT%RESTART_WFN")
2657 :
2658 10 : DO ispin = 1, 2
2659 6 : CALL deallocate_mo_set(restart_mos(ispin))
2660 : END DO
2661 : END DO
2662 : END BLOCK
2663 : END IF
2664 :
2665 : !PDOS related stuff
2666 4 : IF (do_pdos) THEN
2667 :
2668 : !If S^0.5 not yet stored, compute it once and for all
2669 2 : IF (.NOT. ASSOCIATED(xas_tdp_env%matrix_shalf) .AND. do_pdos) THEN
2670 : CALL cp_fm_struct_create(fm_struct, context=blacs_env, para_env=para_env, &
2671 2 : nrow_global=nao, ncol_global=nao)
2672 2 : ALLOCATE (xas_tdp_env%matrix_shalf)
2673 2 : CALL cp_fm_create(xas_tdp_env%matrix_shalf, fm_struct)
2674 2 : CALL cp_fm_create(work_fm, fm_struct)
2675 :
2676 2 : CALL copy_dbcsr_to_fm(matrix_s(1)%matrix, xas_tdp_env%matrix_shalf)
2677 2 : CALL cp_fm_power(xas_tdp_env%matrix_shalf, work_fm, 0.5_dp, EPSILON(0.0_dp), n_dependent)
2678 :
2679 2 : CALL cp_fm_release(work_fm)
2680 2 : CALL cp_fm_struct_release(fm_struct)
2681 : END IF
2682 :
2683 : !Giving some PDOS info
2684 2 : output_unit = cp_logger_get_default_io_unit()
2685 2 : IF (output_unit > 0) THEN
2686 : WRITE (UNIT=output_unit, FMT="(/,T5,A,/,T5,A,/,T5,A)") &
2687 1 : "Computing the PDOS of linear-response orbitals for spectral features analysis", &
2688 1 : "Note: using standard PDOS routines => ignore mentions of KS states and MO ", &
2689 2 : " occupation numbers. Eigenvalues in *.pdos files are excitations energies."
2690 : END IF
2691 :
2692 : !Check on NLUMO
2693 2 : CALL section_vals_val_get(xas_tdp_section, "PRINT%PDOS%NLUMO", i_val=nlumo)
2694 2 : IF (nlumo .NE. 0) THEN
2695 0 : CPWARN("NLUMO is irrelevant for XAS_TDP PDOS. It was overwritten to 0.")
2696 : END IF
2697 2 : CALL section_vals_val_set(xas_tdp_section, "PRINT%PDOS%NLUMO", i_val=0)
2698 : END IF
2699 :
2700 : !CUBES related stuff
2701 4 : IF (do_cubes) THEN
2702 :
2703 2 : print_key => section_vals_get_subs_vals(xas_tdp_section, "PRINT%CUBES")
2704 :
2705 2 : CALL section_vals_val_get(print_key, "CUBES_LU_BOUNDS", i_vals=bounds)
2706 2 : ncubes = bounds(2) - bounds(1) + 1
2707 2 : IF (ncubes > 0) THEN
2708 0 : ALLOCATE (state_list(ncubes))
2709 0 : DO ic = 1, ncubes
2710 0 : state_list(ic) = bounds(1) + ic - 1
2711 : END DO
2712 : END IF
2713 :
2714 2 : IF (.NOT. ASSOCIATED(state_list)) THEN
2715 2 : CALL section_vals_val_get(print_key, "CUBES_LIST", n_rep_val=n_rep)
2716 :
2717 2 : ncubes = 0
2718 4 : DO irep = 1, n_rep
2719 2 : NULLIFY (list)
2720 2 : CALL section_vals_val_get(print_key, "CUBES_LIST", i_rep_val=irep, i_vals=list)
2721 4 : IF (ASSOCIATED(list)) THEN
2722 2 : CALL reallocate(state_list, 1, ncubes + SIZE(list))
2723 4 : DO ic = 1, SIZE(list)
2724 4 : state_list(ncubes + ic) = list(ic)
2725 : END DO
2726 2 : ncubes = ncubes + SIZE(list)
2727 : END IF
2728 : END DO
2729 : END IF
2730 :
2731 2 : IF (.NOT. ASSOCIATED(state_list)) THEN
2732 0 : ncubes = 1
2733 0 : ALLOCATE (state_list(1))
2734 0 : state_list(1) = 1
2735 : END IF
2736 :
2737 2 : CALL section_vals_val_get(print_key, "APPEND", l_val=append_cube)
2738 2 : pos = "REWIND"
2739 2 : IF (append_cube) pos = "APPEND"
2740 :
2741 6 : ALLOCATE (centers(6, ncubes))
2742 18 : centers = 0.0_dp
2743 :
2744 : END IF
2745 :
2746 : !Loop over MOs and spin, one PDOS/CUBE for each
2747 8 : DO ido_mo = 1, ndo_mo
2748 12 : DO ispin = 1, nspins
2749 :
2750 : !need to create a mo set for the LR-orbitals
2751 4 : ALLOCATE (mo_set)
2752 : CALL allocate_mo_set(mo_set, nao=nao, nmo=nmo, nelectron=nmo, n_el_f=REAL(nmo, dp), &
2753 4 : maxocc=1.0_dp, flexible_electron_count=0.0_dp)
2754 4 : CALL init_mo_set(mo_set, fm_ref=mo_coeff, name="PDOS XAS_TDP MOs")
2755 156 : mo_set%eigenvalues(:) = lr_evals(:)
2756 :
2757 : !get the actual coeff => most common case: closed-shell K-edge, can directly take lr_coeffs
2758 4 : IF (nspins == 1 .AND. ndo_mo == 1) THEN
2759 4 : CALL cp_fm_to_fm(lr_coeffs, mo_set%mo_coeff)
2760 : ELSE
2761 0 : DO imo = 1, nmo
2762 : CALL cp_fm_to_fm_submat(msource=lr_coeffs, mtarget=mo_set%mo_coeff, &
2763 : nrow=nao, ncol=1, s_firstrow=1, &
2764 : s_firstcol=(imo - 1)*ndo_so + (ispin - 1)*ndo_mo + ido_mo, &
2765 0 : t_firstrow=1, t_firstcol=imo)
2766 : END DO
2767 : END IF
2768 :
2769 : !naming the output
2770 4 : domon = domo
2771 4 : IF (donor_state%state_type == xas_2p_type) domon = TRIM(domo)//TRIM(ADJUSTL(cp_to_string(ido_mo)))
2772 : xas_mittle = 'xasat'//TRIM(ADJUSTL(cp_to_string(donor_state%at_index)))//'_'// &
2773 4 : TRIM(domon)//'_'//TRIM(excite)
2774 :
2775 4 : IF (do_pdos) THEN
2776 : CALL calculate_projected_dos(mo_set, atomic_kind_set, qs_kind_set, particle_set, &
2777 : qs_env, xas_tdp_section, ispin, xas_mittle, &
2778 2 : external_matrix_shalf=xas_tdp_env%matrix_shalf)
2779 : END IF
2780 :
2781 4 : IF (do_cubes) THEN
2782 : CALL qs_print_cubes(qs_env, mo_set%mo_coeff, ncubes, state_list, centers, &
2783 : print_key=print_key, root=xas_mittle, ispin=ispin, &
2784 2 : file_position=pos)
2785 : END IF
2786 :
2787 : !clean-up
2788 4 : CALL deallocate_mo_set(mo_set)
2789 8 : DEALLOCATE (mo_set)
2790 :
2791 : END DO
2792 : END DO
2793 :
2794 : !clean-up
2795 4 : CALL cp_fm_release(mo_coeff)
2796 4 : CALL cp_fm_struct_release(mo_struct)
2797 4 : IF (do_cubes) DEALLOCATE (centers, state_list)
2798 :
2799 4 : CALL timestop(handle)
2800 :
2801 74 : END SUBROUTINE xas_tdp_post
2802 :
2803 : ! **************************************************************************************************
2804 : !> \brief Computed the LUMOs for the OT eigensolver guesses
2805 : !> \param xas_tdp_env ...
2806 : !> \param xas_tdp_control ...
2807 : !> \param qs_env ...
2808 : !> \note Uses stendard diagonalization. Do not use the stendard make_lumo subroutine as it uses
2809 : !> the OT eigensolver and there is no guarantee that it will converge fast
2810 : ! **************************************************************************************************
2811 20 : SUBROUTINE make_lumo_guess(xas_tdp_env, xas_tdp_control, qs_env)
2812 :
2813 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2814 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2815 : TYPE(qs_environment_type), POINTER :: qs_env
2816 :
2817 : CHARACTER(len=*), PARAMETER :: routineN = 'make_lumo_guess'
2818 :
2819 : INTEGER :: handle, ispin, nao, nelec_spin(2), &
2820 : nlumo(2), nocc(2), nspins
2821 : LOGICAL :: do_os
2822 20 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: evals
2823 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2824 : TYPE(cp_fm_struct_type), POINTER :: fm_struct, lumo_struct
2825 : TYPE(cp_fm_type) :: amatrix, bmatrix, evecs, work_fm
2826 20 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks, matrix_s
2827 : TYPE(mp_para_env_type), POINTER :: para_env
2828 :
2829 20 : NULLIFY (matrix_ks, matrix_s, para_env, blacs_env)
2830 20 : NULLIFY (lumo_struct, fm_struct)
2831 :
2832 20 : CALL timeset(routineN, handle)
2833 :
2834 20 : do_os = xas_tdp_control%do_uks .OR. xas_tdp_control%do_roks
2835 2 : nspins = 1; IF (do_os) nspins = 2
2836 62 : ALLOCATE (xas_tdp_env%lumo_evecs(nspins))
2837 62 : ALLOCATE (xas_tdp_env%lumo_evals(nspins))
2838 : CALL get_qs_env(qs_env, matrix_ks=matrix_ks, matrix_s=matrix_s, nelectron_spin=nelec_spin, &
2839 20 : para_env=para_env, blacs_env=blacs_env)
2840 20 : CALL dbcsr_get_info(matrix_s(1)%matrix, nfullrows_total=nao)
2841 :
2842 20 : IF (do_os) THEN
2843 6 : nlumo = nao - nelec_spin
2844 2 : nocc = nelec_spin
2845 : ELSE
2846 54 : nlumo = nao - nelec_spin(1)/2
2847 54 : nocc = nelec_spin(1)/2
2848 : END IF
2849 :
2850 62 : ALLOCATE (xas_tdp_env%ot_prec(nspins))
2851 :
2852 42 : DO ispin = 1, nspins
2853 :
2854 : !Going through fm to diagonalize
2855 : CALL cp_fm_struct_create(fm_struct, para_env=para_env, context=blacs_env, &
2856 22 : nrow_global=nao, ncol_global=nao)
2857 22 : CALL cp_fm_create(amatrix, fm_struct)
2858 22 : CALL cp_fm_create(bmatrix, fm_struct)
2859 22 : CALL cp_fm_create(evecs, fm_struct)
2860 22 : CALL cp_fm_create(work_fm, fm_struct)
2861 66 : ALLOCATE (evals(nao))
2862 66 : ALLOCATE (xas_tdp_env%lumo_evals(ispin)%array(nlumo(ispin)))
2863 :
2864 22 : CALL copy_dbcsr_to_fm(matrix_ks(ispin)%matrix, amatrix)
2865 22 : CALL copy_dbcsr_to_fm(matrix_s(1)%matrix, bmatrix)
2866 :
2867 : !The actual diagonalization through Cholesky decomposition
2868 22 : CALL cp_fm_geeig(amatrix, bmatrix, evecs, evals, work_fm)
2869 :
2870 : !Storing results
2871 : CALL cp_fm_struct_create(lumo_struct, para_env=para_env, context=blacs_env, &
2872 22 : nrow_global=nao, ncol_global=nlumo(ispin))
2873 22 : CALL cp_fm_create(xas_tdp_env%lumo_evecs(ispin), lumo_struct)
2874 :
2875 : CALL cp_fm_to_fm_submat(evecs, xas_tdp_env%lumo_evecs(ispin), nrow=nao, &
2876 : ncol=nlumo(ispin), s_firstrow=1, s_firstcol=nocc(ispin) + 1, &
2877 22 : t_firstrow=1, t_firstcol=1)
2878 :
2879 1098 : xas_tdp_env%lumo_evals(ispin)%array(1:nlumo(ispin)) = evals(nocc(ispin) + 1:nao)
2880 :
2881 22 : CALL build_ot_spin_prec(evecs, evals, ispin, xas_tdp_env, xas_tdp_control, qs_env)
2882 :
2883 : !clean-up
2884 22 : CALL cp_fm_release(amatrix)
2885 22 : CALL cp_fm_release(bmatrix)
2886 22 : CALL cp_fm_release(evecs)
2887 22 : CALL cp_fm_release(work_fm)
2888 22 : CALL cp_fm_struct_release(fm_struct)
2889 22 : CALL cp_fm_struct_release(lumo_struct)
2890 64 : DEALLOCATE (evals)
2891 : END DO
2892 :
2893 20 : CALL timestop(handle)
2894 :
2895 60 : END SUBROUTINE make_lumo_guess
2896 :
2897 : ! **************************************************************************************************
2898 : !> \brief Builds a preconditioner for the OT eigensolver, based on some heurstics that prioritize
2899 : !> LUMOs with lower eigenvalues
2900 : !> \param evecs all the ground state eigenvectors
2901 : !> \param evals all the ground state eigenvalues
2902 : !> \param ispin ...
2903 : !> \param xas_tdp_env ...
2904 : !> \param xas_tdp_control ...
2905 : !> \param qs_env ...
2906 : !> \note assumes that the preconditioner matrix array is allocated
2907 : ! **************************************************************************************************
2908 22 : SUBROUTINE build_ot_spin_prec(evecs, evals, ispin, xas_tdp_env, xas_tdp_control, qs_env)
2909 :
2910 : TYPE(cp_fm_type), INTENT(IN) :: evecs
2911 : REAL(dp), DIMENSION(:) :: evals
2912 : INTEGER :: ispin
2913 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2914 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2915 : TYPE(qs_environment_type), POINTER :: qs_env
2916 :
2917 : CHARACTER(len=*), PARAMETER :: routineN = 'build_ot_spin_prec'
2918 :
2919 : INTEGER :: handle, nao, nelec_spin(2), nguess, &
2920 : nocc, nspins
2921 : LOGICAL :: do_os
2922 : REAL(dp) :: shift
2923 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: scaling
2924 : TYPE(cp_fm_struct_type), POINTER :: fm_struct
2925 : TYPE(cp_fm_type) :: fm_prec, work_fm
2926 22 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_s
2927 : TYPE(mp_para_env_type), POINTER :: para_env
2928 :
2929 22 : NULLIFY (fm_struct, para_env, matrix_s)
2930 :
2931 22 : CALL timeset(routineN, handle)
2932 :
2933 22 : do_os = xas_tdp_control%do_uks .OR. xas_tdp_control%do_roks
2934 22 : CALL get_qs_env(qs_env, para_env=para_env, nelectron_spin=nelec_spin, matrix_s=matrix_s)
2935 22 : CALL cp_fm_get_info(evecs, nrow_global=nao, matrix_struct=fm_struct)
2936 22 : CALL cp_fm_create(fm_prec, fm_struct)
2937 66 : ALLOCATE (scaling(nao))
2938 22 : nocc = nelec_spin(1)/2
2939 22 : nspins = 1
2940 22 : IF (do_os) THEN
2941 4 : nocc = nelec_spin(ispin)
2942 4 : nspins = 2
2943 : END IF
2944 :
2945 : !rough estimate of the number of required evals
2946 22 : nguess = nao - nocc
2947 22 : IF (xas_tdp_control%n_excited > 0 .AND. xas_tdp_control%n_excited < nguess) THEN
2948 4 : nguess = xas_tdp_control%n_excited/nspins
2949 18 : ELSE IF (xas_tdp_control%e_range > 0.0_dp) THEN
2950 514 : nguess = COUNT(evals(nocc + 1:nao) - evals(nocc + 1) .LE. xas_tdp_control%e_range)
2951 : END IF
2952 :
2953 : !Give max weight to the first LUMOs
2954 540 : scaling(nocc + 1:nocc + nguess) = 100.0_dp
2955 : !Then gradually decrease weight
2956 22 : shift = evals(nocc + 1) - 0.01_dp
2957 602 : scaling(nocc + nguess:nao) = 1.0_dp/(evals(nocc + nguess:nao) - shift)
2958 : !HOMOs do not matter, but need well behaved matrix
2959 616 : scaling(1:nocc) = 1.0_dp
2960 :
2961 : !Building the precond as an fm
2962 22 : CALL cp_fm_create(work_fm, fm_struct)
2963 :
2964 22 : CALL cp_fm_copy_general(evecs, work_fm, para_env)
2965 22 : CALL cp_fm_column_scale(work_fm, scaling)
2966 :
2967 22 : CALL parallel_gemm('N', 'T', nao, nao, nao, 1.0_dp, work_fm, evecs, 0.0_dp, fm_prec)
2968 :
2969 : !Copy into dbcsr format
2970 22 : ALLOCATE (xas_tdp_env%ot_prec(ispin)%matrix)
2971 22 : CALL dbcsr_create(xas_tdp_env%ot_prec(ispin)%matrix, template=matrix_s(1)%matrix, name="OT_PREC")
2972 22 : CALL copy_fm_to_dbcsr(fm_prec, xas_tdp_env%ot_prec(ispin)%matrix)
2973 22 : CALL dbcsr_filter(xas_tdp_env%ot_prec(ispin)%matrix, xas_tdp_control%eps_filter)
2974 :
2975 22 : CALL cp_fm_release(work_fm)
2976 22 : CALL cp_fm_release(fm_prec)
2977 :
2978 22 : CALL timestop(handle)
2979 :
2980 88 : END SUBROUTINE build_ot_spin_prec
2981 :
2982 : ! **************************************************************************************************
2983 : !> \brief Prints GW2X corrected ionization potentials to main output file, including SOC splitting
2984 : !> \param donor_state ...
2985 : !> \param xas_tdp_env ...
2986 : !> \param xas_tdp_control ...
2987 : !> \param qs_env ...
2988 : ! **************************************************************************************************
2989 30 : SUBROUTINE print_xps(donor_state, xas_tdp_env, xas_tdp_control, qs_env)
2990 :
2991 : TYPE(donor_state_type), POINTER :: donor_state
2992 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2993 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2994 : TYPE(qs_environment_type), POINTER :: qs_env
2995 :
2996 : INTEGER :: ido_mo, ispin, nspins, output_unit
2997 30 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: IPs, soc_shifts
2998 :
2999 30 : output_unit = cp_logger_get_default_io_unit()
3000 :
3001 30 : nspins = 1; IF (xas_tdp_control%do_uks .OR. xas_tdp_control%do_roks) nspins = 2
3002 :
3003 120 : ALLOCATE (IPs(SIZE(donor_state%gw2x_evals, 1), SIZE(donor_state%gw2x_evals, 2)))
3004 106 : IPs(:, :) = donor_state%gw2x_evals(:, :)
3005 :
3006 : !IPs in PBCs cannot be trusted because of a lack of a potential reference
3007 30 : IF (.NOT. xas_tdp_control%is_periodic) THEN
3008 :
3009 : !Apply SOC splitting
3010 26 : IF (donor_state%ndo_mo > 1) THEN
3011 : CALL get_soc_splitting(soc_shifts, donor_state, xas_tdp_env, xas_tdp_control, qs_env)
3012 20 : IPs(:, :) = IPs(:, :) + soc_shifts
3013 :
3014 4 : IF (output_unit > 0) THEN
3015 : WRITE (output_unit, FMT="(/,T5,A,F23.6)") &
3016 2 : "Ionization potentials for XPS (GW2X + SOC): ", -IPs(1, 1)*evolt
3017 :
3018 4 : DO ispin = 1, nspins
3019 10 : DO ido_mo = 1, donor_state%ndo_mo
3020 :
3021 6 : IF (ispin == 1 .AND. ido_mo == 1) CYCLE
3022 :
3023 : WRITE (output_unit, FMT="(T5,A,F23.6)") &
3024 8 : " ", -IPs(ido_mo, ispin)*evolt
3025 :
3026 : END DO
3027 : END DO
3028 : END IF
3029 :
3030 : ELSE
3031 :
3032 : ! No SOC, only 1 donor MO per spin
3033 22 : IF (output_unit > 0) THEN
3034 : WRITE (output_unit, FMT="(/,T5,A,F29.6)") &
3035 11 : "Ionization potentials for XPS (GW2X): ", -IPs(1, 1)*evolt
3036 :
3037 11 : IF (nspins == 2) THEN
3038 : WRITE (output_unit, FMT="(T5,A,F29.6)") &
3039 2 : " ", -IPs(1, 2)*evolt
3040 : END IF
3041 : END IF
3042 :
3043 : END IF
3044 : END IF
3045 :
3046 30 : END SUBROUTINE print_xps
3047 :
3048 : ! **************************************************************************************************
3049 : !> \brief Prints the excitation energies and the oscillator strengths for a given donor_state in a file
3050 : !> \param donor_state the donor_state to print
3051 : !> \param xas_tdp_env ...
3052 : !> \param xas_tdp_control ...
3053 : !> \param xas_tdp_section ...
3054 : ! **************************************************************************************************
3055 68 : SUBROUTINE print_xas_tdp_to_file(donor_state, xas_tdp_env, xas_tdp_control, xas_tdp_section)
3056 :
3057 : TYPE(donor_state_type), POINTER :: donor_state
3058 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
3059 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
3060 : TYPE(section_vals_type), POINTER :: xas_tdp_section
3061 :
3062 : INTEGER :: i, output_unit, xas_tdp_unit
3063 : TYPE(cp_logger_type), POINTER :: logger
3064 :
3065 68 : NULLIFY (logger)
3066 68 : logger => cp_get_default_logger()
3067 :
3068 : xas_tdp_unit = cp_print_key_unit_nr(logger, xas_tdp_section, "PRINT%SPECTRUM", &
3069 : extension=".spectrum", file_position="APPEND", &
3070 68 : file_action="WRITE", file_form="FORMATTED")
3071 :
3072 68 : output_unit = cp_logger_get_default_io_unit()
3073 :
3074 68 : IF (output_unit > 0) THEN
3075 : WRITE (output_unit, FMT="(/,T5,A,/)") &
3076 34 : "Calculations done: "
3077 : END IF
3078 :
3079 68 : IF (xas_tdp_control%do_spin_cons) THEN
3080 8 : IF (xas_tdp_unit > 0) THEN
3081 :
3082 : ! Printing the general donor state information
3083 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3084 4 : "==================================================================================", &
3085 4 : "XAS TDP open-shell spin-conserving (no SOC) excitations for DONOR STATE: ", &
3086 4 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3087 4 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3088 4 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3089 8 : "=================================================================================="
3090 :
3091 : ! Simply dump the excitation energies/ oscillator strength as they come
3092 :
3093 4 : IF (xas_tdp_control%do_quad) THEN
3094 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3095 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3096 0 : DO i = 1, SIZE(donor_state%sc_evals)
3097 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3098 0 : i, donor_state%sc_evals(i)*evolt, donor_state%osc_str(i, 4), &
3099 0 : donor_state%quad_osc_str(i)
3100 : END DO
3101 4 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3102 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3103 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3104 0 : DO i = 1, SIZE(donor_state%sc_evals)
3105 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3106 0 : i, donor_state%sc_evals(i)*evolt, donor_state%osc_str(i, 4), &
3107 0 : donor_state%osc_str(i, 1), donor_state%osc_str(i, 2), donor_state%osc_str(i, 3)
3108 : END DO
3109 4 : ELSE IF (xas_tdp_control%spin_dip) THEN
3110 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3111 0 : " Index Excitation energy (eV) fosc dipole (a.u.) alpha-comp beta-comp"
3112 0 : DO i = 1, SIZE(donor_state%sc_evals)
3113 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6)") &
3114 0 : i, donor_state%sc_evals(i)*evolt, donor_state%osc_str(i, 4), &
3115 0 : donor_state%alpha_osc(i, 4), donor_state%beta_osc(i, 4)
3116 : END DO
3117 : ELSE
3118 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3119 4 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3120 108 : DO i = 1, SIZE(donor_state%sc_evals)
3121 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3122 108 : i, donor_state%sc_evals(i)*evolt, donor_state%osc_str(i, 4)
3123 : END DO
3124 : END IF
3125 :
3126 4 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3127 : END IF !xas_tdp_unit > 0
3128 :
3129 8 : IF (output_unit > 0) THEN
3130 : WRITE (output_unit, FMT="(T5,A,F17.6)") &
3131 4 : "First spin-conserving XAS excitation energy (eV): ", donor_state%sc_evals(1)*evolt
3132 : END IF
3133 :
3134 : END IF ! do_spin_cons
3135 :
3136 68 : IF (xas_tdp_control%do_spin_flip) THEN
3137 2 : IF (xas_tdp_unit > 0) THEN
3138 :
3139 : ! Printing the general donor state information
3140 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3141 1 : "==================================================================================", &
3142 1 : "XAS TDP open-shell spin-flip (no SOC) excitations for DONOR STATE: ", &
3143 1 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3144 1 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3145 1 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3146 2 : "=================================================================================="
3147 :
3148 : ! Simply dump the excitation energies/ oscillator strength as they come
3149 :
3150 1 : IF (xas_tdp_control%do_quad) THEN
3151 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3152 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3153 0 : DO i = 1, SIZE(donor_state%sf_evals)
3154 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3155 0 : i, donor_state%sf_evals(i)*evolt, 0.0_dp, 0.0_dp !spin-forbidden !
3156 : END DO
3157 1 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3158 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3159 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3160 0 : DO i = 1, SIZE(donor_state%sf_evals)
3161 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3162 0 : i, donor_state%sf_evals(i)*evolt, 0.0_dp, 0.0_dp, 0.0_dp, 0.0_dp
3163 : END DO
3164 1 : ELSE IF (xas_tdp_control%spin_dip) THEN
3165 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3166 0 : " Index Excitation energy (eV) fosc dipole (a.u.) alpha-comp beta-comp"
3167 0 : DO i = 1, SIZE(donor_state%sf_evals)
3168 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6)") &
3169 0 : i, donor_state%sf_evals(i)*evolt, 0.0_dp, 0.0_dp, 0.0_dp
3170 : END DO
3171 : ELSE
3172 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3173 1 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3174 13 : DO i = 1, SIZE(donor_state%sf_evals)
3175 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3176 13 : i, donor_state%sf_evals(i)*evolt, 0.0_dp
3177 : END DO
3178 : END IF
3179 :
3180 1 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3181 : END IF !xas_tdp_unit
3182 :
3183 2 : IF (output_unit > 0) THEN
3184 : WRITE (output_unit, FMT="(T5,A,F23.6)") &
3185 1 : "First spin-flip XAS excitation energy (eV): ", donor_state%sf_evals(1)*evolt
3186 : END IF
3187 : END IF ! do_spin_flip
3188 :
3189 68 : IF (xas_tdp_control%do_singlet) THEN
3190 60 : IF (xas_tdp_unit > 0) THEN
3191 :
3192 : ! Printing the general donor state information
3193 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3194 30 : "==================================================================================", &
3195 30 : "XAS TDP singlet excitations (no SOC) for DONOR STATE: ", &
3196 30 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3197 30 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3198 30 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3199 60 : "=================================================================================="
3200 :
3201 : ! Simply dump the excitation energies/ oscillator strength as they come
3202 :
3203 30 : IF (xas_tdp_control%do_quad) THEN
3204 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3205 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3206 0 : DO i = 1, SIZE(donor_state%sg_evals)
3207 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3208 0 : i, donor_state%sg_evals(i)*evolt, donor_state%osc_str(i, 4), &
3209 0 : donor_state%quad_osc_str(i)
3210 : END DO
3211 30 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3212 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3213 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3214 0 : DO i = 1, SIZE(donor_state%sg_evals)
3215 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3216 0 : i, donor_state%sg_evals(i)*evolt, donor_state%osc_str(i, 4), &
3217 0 : donor_state%osc_str(i, 1), donor_state%osc_str(i, 2), donor_state%osc_str(i, 3)
3218 : END DO
3219 : ELSE
3220 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3221 30 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3222 438 : DO i = 1, SIZE(donor_state%sg_evals)
3223 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3224 438 : i, donor_state%sg_evals(i)*evolt, donor_state%osc_str(i, 4)
3225 : END DO
3226 : END IF
3227 :
3228 30 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3229 : END IF !xas_tdp_unit
3230 :
3231 60 : IF (output_unit > 0) THEN
3232 : WRITE (output_unit, FMT="(T5,A,F25.6)") &
3233 30 : "First singlet XAS excitation energy (eV): ", donor_state%sg_evals(1)*evolt
3234 : END IF
3235 : END IF ! do_singlet
3236 :
3237 68 : IF (xas_tdp_control%do_triplet) THEN
3238 2 : IF (xas_tdp_unit > 0) THEN
3239 :
3240 : ! Printing the general donor state information
3241 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3242 1 : "==================================================================================", &
3243 1 : "XAS TDP triplet excitations (no SOC) for DONOR STATE: ", &
3244 1 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3245 1 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3246 1 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3247 2 : "=================================================================================="
3248 :
3249 : ! Simply dump the excitation energies/ oscillator strength as they come
3250 :
3251 1 : IF (xas_tdp_control%do_quad) THEN
3252 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3253 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3254 0 : DO i = 1, SIZE(donor_state%tp_evals)
3255 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3256 0 : i, donor_state%tp_evals(i)*evolt, 0.0_dp, 0.0_dp !spin-forbidden !
3257 : END DO
3258 1 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3259 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3260 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3261 0 : DO i = 1, SIZE(donor_state%tp_evals)
3262 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3263 0 : i, donor_state%tp_evals(i)*evolt, 0.0_dp, 0.0_dp, 0.0_dp, 0.0_dp
3264 : END DO
3265 1 : ELSE IF (xas_tdp_control%spin_dip) THEN
3266 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3267 0 : " Index Excitation energy (eV) fosc dipole (a.u.) alpha-comp beta-comp"
3268 0 : DO i = 1, SIZE(donor_state%tp_evals)
3269 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6)") &
3270 0 : i, donor_state%tp_evals(i)*evolt, 0.0_dp, 0.0_dp, 0.0_dp
3271 : END DO
3272 : ELSE
3273 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3274 1 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3275 13 : DO i = 1, SIZE(donor_state%tp_evals)
3276 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3277 13 : i, donor_state%tp_evals(i)*evolt, 0.0_dp
3278 : END DO
3279 : END IF
3280 :
3281 1 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3282 : END IF !xas_tdp_unit
3283 :
3284 2 : IF (output_unit > 0) THEN
3285 : WRITE (output_unit, FMT="(T5,A,F25.6)") &
3286 1 : "First triplet XAS excitation energy (eV): ", donor_state%tp_evals(1)*evolt
3287 : END IF
3288 : END IF ! do_triplet
3289 :
3290 68 : IF (xas_tdp_control%do_soc .AND. donor_state%state_type == xas_2p_type) THEN
3291 4 : IF (xas_tdp_unit > 0) THEN
3292 :
3293 : ! Printing the general donor state information
3294 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3295 2 : "==================================================================================", &
3296 2 : "XAS TDP excitations after spin-orbit coupling for DONOR STATE: ", &
3297 2 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3298 2 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3299 2 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3300 4 : "=================================================================================="
3301 :
3302 : ! Simply dump the excitation energies/ oscillator strength as they come
3303 2 : IF (xas_tdp_control%do_quad) THEN
3304 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3305 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3306 0 : DO i = 1, SIZE(donor_state%soc_evals)
3307 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3308 0 : i, donor_state%soc_evals(i)*evolt, donor_state%soc_osc_str(i, 4), &
3309 0 : donor_state%soc_quad_osc_str(i)
3310 : END DO
3311 2 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3312 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3313 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3314 0 : DO i = 1, SIZE(donor_state%soc_evals)
3315 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3316 0 : i, donor_state%soc_evals(i)*evolt, donor_state%soc_osc_str(i, 4), &
3317 0 : donor_state%soc_osc_str(i, 1), donor_state%soc_osc_str(i, 2), donor_state%soc_osc_str(i, 3)
3318 : END DO
3319 : ELSE
3320 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3321 2 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3322 74 : DO i = 1, SIZE(donor_state%soc_evals)
3323 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3324 74 : i, donor_state%soc_evals(i)*evolt, donor_state%soc_osc_str(i, 4)
3325 : END DO
3326 : END IF
3327 :
3328 2 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3329 : END IF !xas_tdp_unit
3330 :
3331 4 : IF (output_unit > 0) THEN
3332 : WRITE (output_unit, FMT="(T5,A,F29.6)") &
3333 2 : "First SOC XAS excitation energy (eV): ", donor_state%soc_evals(1)*evolt
3334 : END IF
3335 : END IF !do_soc
3336 :
3337 68 : CALL cp_print_key_finished_output(xas_tdp_unit, logger, xas_tdp_section, "PRINT%SPECTRUM")
3338 :
3339 68 : END SUBROUTINE print_xas_tdp_to_file
3340 :
3341 : ! **************************************************************************************************
3342 : !> \brief Prints the donor_state and excitation_type info into a RESTART file for cheap PDOS and/or
3343 : !> CUBE printing without expensive computation
3344 : !> \param ex_type singlet, triplet, etc.
3345 : !> \param donor_state ...
3346 : !> \param xas_tdp_section ...
3347 : !> \param qs_env ...
3348 : ! **************************************************************************************************
3349 76 : SUBROUTINE write_donor_state_restart(ex_type, donor_state, xas_tdp_section, qs_env)
3350 :
3351 : INTEGER, INTENT(IN) :: ex_type
3352 : TYPE(donor_state_type), POINTER :: donor_state
3353 : TYPE(section_vals_type), POINTER :: xas_tdp_section
3354 : TYPE(qs_environment_type), POINTER :: qs_env
3355 :
3356 : CHARACTER(len=*), PARAMETER :: routineN = 'write_donor_state_restart'
3357 :
3358 : CHARACTER(len=default_path_length) :: filename
3359 : CHARACTER(len=default_string_length) :: domo, excite, my_middle
3360 : INTEGER :: ex_atom, handle, ispin, nao, ndo_mo, &
3361 : nex, nspins, output_unit, rst_unit, &
3362 : state_type
3363 72 : INTEGER, DIMENSION(:, :), POINTER :: mo_indices
3364 : LOGICAL :: do_print
3365 72 : REAL(dp), DIMENSION(:), POINTER :: lr_evals
3366 : TYPE(cp_fm_type), POINTER :: lr_coeffs
3367 : TYPE(cp_logger_type), POINTER :: logger
3368 72 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
3369 : TYPE(section_vals_type), POINTER :: print_key
3370 :
3371 72 : NULLIFY (logger, lr_coeffs, lr_evals, print_key, mos)
3372 :
3373 : !Initialization
3374 144 : logger => cp_get_default_logger()
3375 72 : do_print = .FALSE.
3376 72 : IF (BTEST(cp_print_key_should_output(logger%iter_info, xas_tdp_section, &
3377 : "PRINT%RESTART", used_print_key=print_key), cp_p_file)) do_print = .TRUE.
3378 :
3379 70 : IF (.NOT. do_print) RETURN
3380 :
3381 2 : CALL timeset(routineN, handle)
3382 :
3383 2 : output_unit = cp_logger_get_default_io_unit()
3384 :
3385 : !Get general info
3386 2 : SELECT CASE (ex_type)
3387 : CASE (tddfpt_spin_cons)
3388 0 : lr_evals => donor_state%sc_evals
3389 0 : lr_coeffs => donor_state%sc_coeffs
3390 0 : excite = "spincons"
3391 0 : nspins = 2
3392 : CASE (tddfpt_spin_flip)
3393 0 : lr_evals => donor_state%sf_evals
3394 0 : lr_coeffs => donor_state%sf_coeffs
3395 0 : excite = "spinflip"
3396 0 : nspins = 2
3397 : CASE (tddfpt_singlet)
3398 2 : lr_evals => donor_state%sg_evals
3399 2 : lr_coeffs => donor_state%sg_coeffs
3400 2 : excite = "singlet"
3401 2 : nspins = 1
3402 : CASE (tddfpt_triplet)
3403 0 : lr_evals => donor_state%tp_evals
3404 0 : lr_coeffs => donor_state%tp_coeffs
3405 0 : excite = "triplet"
3406 2 : nspins = 1
3407 : END SELECT
3408 :
3409 4 : SELECT CASE (donor_state%state_type)
3410 : CASE (xas_1s_type)
3411 2 : domo = "1s"
3412 : CASE (xas_2s_type)
3413 0 : domo = "2s"
3414 : CASE (xas_2p_type)
3415 2 : domo = "2p"
3416 : END SELECT
3417 :
3418 2 : ndo_mo = donor_state%ndo_mo
3419 2 : nex = SIZE(lr_evals)
3420 2 : CALL cp_fm_get_info(lr_coeffs, nrow_global=nao)
3421 2 : state_type = donor_state%state_type
3422 2 : ex_atom = donor_state%at_index
3423 2 : mo_indices => donor_state%mo_indices
3424 :
3425 : !Opening restart file
3426 2 : rst_unit = -1
3427 2 : my_middle = 'xasat'//TRIM(ADJUSTL(cp_to_string(ex_atom)))//'_'//TRIM(domo)//'_'//TRIM(excite)
3428 : rst_unit = cp_print_key_unit_nr(logger, xas_tdp_section, "PRINT%RESTART", extension=".rst", &
3429 : file_status="REPLACE", file_action="WRITE", &
3430 2 : file_form="UNFORMATTED", middle_name=TRIM(my_middle))
3431 :
3432 : filename = cp_print_key_generate_filename(logger, print_key, middle_name=TRIM(my_middle), &
3433 2 : extension=".rst", my_local=.FALSE.)
3434 :
3435 2 : IF (output_unit > 0) THEN
3436 : WRITE (UNIT=output_unit, FMT="(/,T5,A,/T5,A,A,A)") &
3437 1 : "Linear-response orbitals and excitation energies are written in: ", &
3438 2 : '"', TRIM(filename), '"'
3439 : END IF
3440 :
3441 : !Writing
3442 2 : IF (rst_unit > 0) THEN
3443 1 : WRITE (rst_unit) ex_atom, state_type, ndo_mo, ex_type
3444 1 : WRITE (rst_unit) nao, nex, nspins
3445 1 : WRITE (rst_unit) mo_indices(:, :)
3446 1 : WRITE (rst_unit) lr_evals(:)
3447 : END IF
3448 2 : CALL cp_fm_write_unformatted(lr_coeffs, rst_unit)
3449 :
3450 : !The MOs as well (because the may have been localized)
3451 2 : CALL get_qs_env(qs_env, mos=mos)
3452 4 : DO ispin = 1, nspins
3453 4 : CALL cp_fm_write_unformatted(mos(ispin)%mo_coeff, rst_unit)
3454 : END DO
3455 :
3456 : !closing
3457 2 : CALL cp_print_key_finished_output(rst_unit, logger, xas_tdp_section, "PRINT%RESTART")
3458 :
3459 2 : CALL timestop(handle)
3460 :
3461 72 : END SUBROUTINE write_donor_state_restart
3462 :
3463 : ! **************************************************************************************************
3464 : !> \brief Reads donor_state info from a restart file
3465 : !> \param donor_state the pre-allocated donor_state
3466 : !> \param ex_type the excitations stored in this specific file
3467 : !> \param filename the restart file to read from
3468 : !> \param qs_env ...
3469 : ! **************************************************************************************************
3470 2 : SUBROUTINE read_donor_state_restart(donor_state, ex_type, filename, qs_env)
3471 :
3472 : TYPE(donor_state_type), POINTER :: donor_state
3473 : INTEGER, INTENT(OUT) :: ex_type
3474 : CHARACTER(len=*), INTENT(IN) :: filename
3475 : TYPE(qs_environment_type), POINTER :: qs_env
3476 :
3477 : CHARACTER(len=*), PARAMETER :: routineN = 'read_donor_state_restart'
3478 :
3479 : INTEGER :: handle, ispin, nao, nex, nspins, &
3480 : output_unit, read_params(7), rst_unit
3481 2 : INTEGER, DIMENSION(:, :), POINTER :: mo_indices
3482 : LOGICAL :: file_exists
3483 2 : REAL(dp), DIMENSION(:), POINTER :: lr_evals
3484 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
3485 : TYPE(cp_fm_struct_type), POINTER :: fm_struct
3486 : TYPE(cp_fm_type), POINTER :: lr_coeffs
3487 2 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
3488 : TYPE(mp_comm_type) :: group
3489 : TYPE(mp_para_env_type), POINTER :: para_env
3490 :
3491 2 : NULLIFY (lr_evals, lr_coeffs, para_env, fm_struct, blacs_env, mos)
3492 :
3493 2 : CALL timeset(routineN, handle)
3494 :
3495 2 : output_unit = cp_logger_get_default_io_unit()
3496 2 : CPASSERT(ASSOCIATED(donor_state))
3497 2 : CALL get_qs_env(qs_env, para_env=para_env, blacs_env=blacs_env)
3498 2 : group = para_env
3499 :
3500 2 : file_exists = .FALSE.
3501 2 : rst_unit = -1
3502 :
3503 2 : IF (para_env%is_source()) THEN
3504 :
3505 1 : INQUIRE (FILE=filename, EXIST=file_exists)
3506 1 : IF (.NOT. file_exists) CPABORT("Trying to read non-existing XAS_TDP restart file")
3507 :
3508 : CALL open_file(file_name=TRIM(filename), file_action="READ", file_form="UNFORMATTED", &
3509 1 : file_position="REWIND", file_status="OLD", unit_number=rst_unit)
3510 : END IF
3511 :
3512 2 : IF (output_unit > 0) THEN
3513 : WRITE (UNIT=output_unit, FMT="(/,T5,A,/,T5,A,A,A)") &
3514 1 : "Reading linear-response orbitals and excitation energies from file: ", &
3515 2 : '"', filename, '"'
3516 : END IF
3517 :
3518 : !read general params
3519 2 : IF (rst_unit > 0) THEN
3520 1 : READ (rst_unit) read_params(1:4)
3521 1 : READ (rst_unit) read_params(5:7)
3522 : END IF
3523 2 : CALL group%bcast(read_params)
3524 2 : donor_state%at_index = read_params(1)
3525 2 : donor_state%state_type = read_params(2)
3526 2 : donor_state%ndo_mo = read_params(3)
3527 2 : ex_type = read_params(4)
3528 2 : nao = read_params(5)
3529 2 : nex = read_params(6)
3530 2 : nspins = read_params(7)
3531 :
3532 8 : ALLOCATE (mo_indices(donor_state%ndo_mo, nspins))
3533 2 : IF (rst_unit > 0) THEN
3534 1 : READ (rst_unit) mo_indices(1:donor_state%ndo_mo, 1:nspins)
3535 : END IF
3536 10 : CALL group%bcast(mo_indices)
3537 2 : donor_state%mo_indices => mo_indices
3538 :
3539 : !read evals
3540 6 : ALLOCATE (lr_evals(nex))
3541 2 : IF (rst_unit > 0) READ (rst_unit) lr_evals(1:nex)
3542 78 : CALL group%bcast(lr_evals)
3543 :
3544 : !read evecs
3545 : CALL cp_fm_struct_create(fm_struct, context=blacs_env, para_env=para_env, &
3546 2 : nrow_global=nao, ncol_global=nex*donor_state%ndo_mo*nspins)
3547 2 : ALLOCATE (lr_coeffs)
3548 2 : CALL cp_fm_create(lr_coeffs, fm_struct)
3549 2 : CALL cp_fm_read_unformatted(lr_coeffs, rst_unit)
3550 2 : CALL cp_fm_struct_release(fm_struct)
3551 :
3552 : !read MO coeffs and replace in qs_env
3553 2 : CALL get_qs_env(qs_env, mos=mos)
3554 4 : DO ispin = 1, nspins
3555 4 : CALL cp_fm_read_unformatted(mos(ispin)%mo_coeff, rst_unit)
3556 : END DO
3557 :
3558 : !closing file
3559 2 : IF (para_env%is_source()) THEN
3560 1 : CALL close_file(unit_number=rst_unit)
3561 : END IF
3562 :
3563 : !case study on excitation type
3564 2 : SELECT CASE (ex_type)
3565 : CASE (tddfpt_spin_cons)
3566 0 : donor_state%sc_evals => lr_evals
3567 0 : donor_state%sc_coeffs => lr_coeffs
3568 : CASE (tddfpt_spin_flip)
3569 0 : donor_state%sf_evals => lr_evals
3570 0 : donor_state%sf_coeffs => lr_coeffs
3571 : CASE (tddfpt_singlet)
3572 2 : donor_state%sg_evals => lr_evals
3573 2 : donor_state%sg_coeffs => lr_coeffs
3574 : CASE (tddfpt_triplet)
3575 0 : donor_state%tp_evals => lr_evals
3576 2 : donor_state%tp_coeffs => lr_coeffs
3577 : END SELECT
3578 :
3579 2 : CALL timestop(handle)
3580 :
3581 4 : END SUBROUTINE read_donor_state_restart
3582 :
3583 : ! **************************************************************************************************
3584 : !> \brief Checks whether this is a restart calculation and runs it if so
3585 : !> \param rst_filename the file to read for restart
3586 : !> \param xas_tdp_section ...
3587 : !> \param qs_env ...
3588 : ! **************************************************************************************************
3589 4 : SUBROUTINE restart_calculation(rst_filename, xas_tdp_section, qs_env)
3590 :
3591 : CHARACTER(len=*), INTENT(IN) :: rst_filename
3592 : TYPE(section_vals_type), POINTER :: xas_tdp_section
3593 : TYPE(qs_environment_type), POINTER :: qs_env
3594 :
3595 : INTEGER :: ex_type
3596 : TYPE(donor_state_type), POINTER :: donor_state
3597 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
3598 :
3599 2 : NULLIFY (xas_tdp_env, donor_state)
3600 :
3601 : !create a donor_state that we fill with the information we read
3602 2 : ALLOCATE (donor_state)
3603 2 : CALL donor_state_create(donor_state)
3604 2 : CALL read_donor_state_restart(donor_state, ex_type, rst_filename, qs_env)
3605 :
3606 : !create a dummy xas_tdp_env and compute the post XAS_TDP stuff
3607 2 : CALL xas_tdp_env_create(xas_tdp_env)
3608 2 : CALL xas_tdp_post(ex_type, donor_state, xas_tdp_env, xas_tdp_section, qs_env)
3609 :
3610 : !clean-up
3611 2 : CALL xas_tdp_env_release(xas_tdp_env)
3612 2 : CALL free_ds_memory(donor_state)
3613 2 : DEALLOCATE (donor_state%mo_indices)
3614 2 : DEALLOCATE (donor_state)
3615 :
3616 2 : END SUBROUTINE restart_calculation
3617 :
3618 : END MODULE xas_tdp_methods
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