Line data Source code
1 : !--------------------------------------------------------------------------------------------------!
2 : ! CP2K: A general program to perform molecular dynamics simulations !
3 : ! Copyright 2000-2024 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_operations, ONLY: copy_dbcsr_to_fm,&
30 : copy_fm_to_dbcsr,&
31 : cp_dbcsr_sm_fm_multiply
32 : USE cp_files, ONLY: close_file,&
33 : open_file
34 : USE cp_fm_basic_linalg, ONLY: cp_fm_column_scale
35 : USE cp_fm_diag, ONLY: cp_fm_geeig,&
36 : cp_fm_power,&
37 : cp_fm_syevd
38 : USE cp_fm_struct, ONLY: cp_fm_struct_create,&
39 : cp_fm_struct_release,&
40 : cp_fm_struct_type
41 : USE cp_fm_types, ONLY: &
42 : cp_fm_copy_general, cp_fm_create, cp_fm_get_diag, cp_fm_get_info, cp_fm_get_submatrix, &
43 : cp_fm_read_unformatted, cp_fm_release, cp_fm_set_all, cp_fm_to_fm, cp_fm_to_fm_submat, &
44 : cp_fm_type, cp_fm_write_unformatted
45 : USE cp_log_handling, ONLY: cp_get_default_logger,&
46 : cp_logger_get_default_io_unit,&
47 : cp_logger_type,&
48 : cp_to_string
49 : USE cp_output_handling, ONLY: cp_p_file,&
50 : cp_print_key_finished_output,&
51 : cp_print_key_generate_filename,&
52 : cp_print_key_should_output,&
53 : cp_print_key_unit_nr,&
54 : debug_print_level
55 : USE dbcsr_api, ONLY: &
56 : dbcsr_add_on_diag, dbcsr_complete_redistribute, dbcsr_copy, dbcsr_create, dbcsr_filter, &
57 : dbcsr_finalize, dbcsr_get_info, dbcsr_get_occupation, dbcsr_multiply, dbcsr_p_type, &
58 : dbcsr_release, dbcsr_set, dbcsr_type, dbcsr_type_antisymmetric, dbcsr_type_no_symmetry, &
59 : dbcsr_type_symmetric
60 : USE input_constants, ONLY: &
61 : do_admm_purify_cauchy_subspace, do_admm_purify_mo_diag, do_admm_purify_none, do_loc_none, &
62 : do_potential_coulomb, do_potential_id, do_potential_short, do_potential_truncated, &
63 : op_loc_berry, state_loc_list, tddfpt_singlet, tddfpt_spin_cons, tddfpt_spin_flip, &
64 : tddfpt_triplet, xas_1s_type, xas_2p_type, xas_2s_type, xas_dip_len, xas_dip_vel, &
65 : xas_not_excited, xas_tdp_by_index, xas_tdp_by_kind
66 : USE input_cp2k_loc, ONLY: create_localize_section
67 : USE input_section_types, ONLY: section_release,&
68 : section_type,&
69 : section_vals_create,&
70 : section_vals_get_subs_vals,&
71 : section_vals_type,&
72 : section_vals_val_get,&
73 : section_vals_val_set
74 : USE kinds, ONLY: default_path_length,&
75 : default_string_length,&
76 : dp
77 : USE libint_wrapper, ONLY: cp_libint_static_init
78 : USE machine, ONLY: m_flush
79 : USE mathlib, ONLY: get_diag
80 : USE memory_utilities, ONLY: reallocate
81 : USE message_passing, ONLY: mp_comm_type,&
82 : mp_para_env_type
83 : USE parallel_gemm_api, ONLY: parallel_gemm
84 : USE parallel_rng_types, ONLY: UNIFORM,&
85 : rng_stream_type
86 : USE particle_methods, ONLY: get_particle_set
87 : USE particle_types, ONLY: particle_type
88 : USE periodic_table, ONLY: ptable
89 : USE physcon, ONLY: a_fine,&
90 : angstrom,&
91 : evolt
92 : USE qs_environment_types, ONLY: get_qs_env,&
93 : qs_environment_type
94 : USE qs_interactions, ONLY: init_interaction_radii_orb_basis
95 : USE qs_kind_types, ONLY: get_qs_kind,&
96 : qs_kind_type
97 : USE qs_loc_main, ONLY: qs_loc_driver
98 : USE qs_loc_methods, ONLY: centers_spreads_berry,&
99 : qs_print_cubes
100 : USE qs_loc_types, ONLY: get_qs_loc_env,&
101 : localized_wfn_control_create,&
102 : localized_wfn_control_type,&
103 : qs_loc_env_create,&
104 : qs_loc_env_release,&
105 : qs_loc_env_type
106 : USE qs_loc_utils, ONLY: qs_loc_control_init,&
107 : qs_loc_env_init,&
108 : set_loc_centers
109 : USE qs_mo_io, ONLY: write_mo_set_low
110 : USE qs_mo_methods, ONLY: calculate_subspace_eigenvalues
111 : USE qs_mo_types, ONLY: allocate_mo_set,&
112 : deallocate_mo_set,&
113 : duplicate_mo_set,&
114 : get_mo_set,&
115 : init_mo_set,&
116 : mo_set_type
117 : USE qs_operators_ao, ONLY: p_xyz_ao,&
118 : rRc_xyz_ao
119 : USE qs_pdos, ONLY: calculate_projected_dos
120 : USE qs_rho_types, ONLY: qs_rho_get,&
121 : qs_rho_type
122 : USE qs_scf_types, ONLY: ot_method_nr
123 : USE util, ONLY: get_limit,&
124 : locate,&
125 : sort_unique
126 : USE xas_methods, ONLY: calc_stogto_overlap
127 : USE xas_tdp_atom, ONLY: init_xas_atom_env,&
128 : integrate_fxc_atoms,&
129 : integrate_soc_atoms
130 : USE xas_tdp_correction, ONLY: GW2X_shift,&
131 : get_soc_splitting
132 : USE xas_tdp_integrals, ONLY: compute_ri_3c_coulomb,&
133 : compute_ri_3c_exchange,&
134 : compute_ri_coulomb2_int,&
135 : compute_ri_exchange2_int
136 : USE xas_tdp_types, ONLY: &
137 : donor_state_create, donor_state_type, free_ds_memory, free_exat_memory, &
138 : read_xas_tdp_control, set_donor_state, set_xas_tdp_env, xas_atom_env_create, &
139 : xas_atom_env_release, xas_atom_env_type, xas_tdp_control_create, xas_tdp_control_release, &
140 : xas_tdp_control_type, xas_tdp_env_create, xas_tdp_env_release, xas_tdp_env_type
141 : USE xas_tdp_utils, ONLY: include_os_soc,&
142 : include_rcs_soc,&
143 : setup_xas_tdp_prob,&
144 : solve_xas_tdp_prob
145 : USE xc_write_output, ONLY: xc_write
146 : #include "./base/base_uses.f90"
147 :
148 : IMPLICIT NONE
149 : PRIVATE
150 :
151 : CHARACTER(len=*), PARAMETER, PRIVATE :: moduleN = 'xas_tdp_methods'
152 :
153 : PUBLIC :: xas_tdp, xas_tdp_init
154 :
155 : CONTAINS
156 :
157 : ! **************************************************************************************************
158 : !> \brief Driver for XAS TDDFT calculations.
159 : !> \param qs_env the inherited qs_environment
160 : !> \author AB
161 : !> \note Empty for now...
162 : ! **************************************************************************************************
163 100 : SUBROUTINE xas_tdp(qs_env)
164 :
165 : TYPE(qs_environment_type), POINTER :: qs_env
166 :
167 : CHARACTER(len=*), PARAMETER :: routineN = 'xas_tdp'
168 :
169 : CHARACTER(default_string_length) :: rst_filename
170 : INTEGER :: handle, n_rep, output_unit
171 : LOGICAL :: do_restart
172 : TYPE(section_vals_type), POINTER :: xas_tdp_section
173 :
174 50 : CALL timeset(routineN, handle)
175 :
176 : ! Logger initialization and XAS TDP banner printing
177 50 : NULLIFY (xas_tdp_section)
178 50 : xas_tdp_section => section_vals_get_subs_vals(qs_env%input, "DFT%XAS_TDP")
179 50 : output_unit = cp_logger_get_default_io_unit()
180 :
181 50 : IF (output_unit > 0) THEN
182 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/,T3,A,/,T3,A,/,T3,A,/)") &
183 25 : "!===========================================================================!", &
184 25 : "! XAS TDP !", &
185 25 : "! Starting TDDFPT driven X-rays absorption spectroscopy calculations !", &
186 50 : "!===========================================================================!"
187 : END IF
188 :
189 50 : CALL cite_reference(Bussy2021a)
190 :
191 : ! Check whether this is a restart calculation, i.e. is a restart file is provided
192 50 : CALL section_vals_val_get(xas_tdp_section, "RESTART_FROM_FILE", n_rep_val=n_rep)
193 :
194 50 : IF (n_rep < 1) THEN
195 : do_restart = .FALSE.
196 : ELSE
197 2 : CALL section_vals_val_get(xas_tdp_section, "RESTART_FROM_FILE", c_val=rst_filename)
198 : do_restart = .TRUE.
199 : END IF
200 :
201 : ! Restart the calculation if needed
202 : IF (do_restart) THEN
203 :
204 2 : IF (output_unit > 0) THEN
205 : WRITE (UNIT=output_unit, FMT="(/,T3,A)") &
206 1 : "# This is a RESTART calculation for PDOS and/or CUBE printing"
207 : END IF
208 :
209 2 : CALL restart_calculation(rst_filename, xas_tdp_section, qs_env)
210 :
211 : ! or run the core XAS_TDP routine if not
212 : ELSE
213 48 : CALL xas_tdp_core(xas_tdp_section, qs_env)
214 : END IF
215 :
216 50 : IF (output_unit > 0) THEN
217 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/,T3,A,/,T3,A,/)") &
218 25 : "!===========================================================================!", &
219 25 : "! End of TDDFPT driven X-rays absorption spectroscopy calculations !", &
220 50 : "!===========================================================================!"
221 : END IF
222 :
223 50 : CALL timestop(handle)
224 :
225 50 : END SUBROUTINE xas_tdp
226 :
227 : ! **************************************************************************************************
228 : !> \brief The core workflow of the XAS_TDP method
229 : !> \param xas_tdp_section the input values for XAS_TDP
230 : !> \param qs_env ...
231 : ! **************************************************************************************************
232 48 : SUBROUTINE xas_tdp_core(xas_tdp_section, qs_env)
233 :
234 : TYPE(section_vals_type), POINTER :: xas_tdp_section
235 : TYPE(qs_environment_type), POINTER :: qs_env
236 :
237 : CHARACTER(LEN=default_string_length) :: kind_name
238 : INTEGER :: batch_size, bo(2), current_state_index, iat, iatom, ibatch, ikind, ispin, istate, &
239 : nbatch, nex_atom, output_unit, tmp_index
240 48 : INTEGER, ALLOCATABLE, DIMENSION(:) :: batch_atoms, ex_atoms_of_kind
241 48 : INTEGER, DIMENSION(:), POINTER :: atoms_of_kind
242 : LOGICAL :: do_os, end_of_batch, unique
243 : TYPE(admm_type), POINTER :: admm_env
244 48 : TYPE(atomic_kind_type), DIMENSION(:), POINTER :: atomic_kind_set
245 48 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks
246 : TYPE(dft_control_type), POINTER :: dft_control
247 : TYPE(donor_state_type), POINTER :: current_state
248 : TYPE(gto_basis_set_type), POINTER :: tmp_basis
249 48 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
250 : TYPE(xas_atom_env_type), POINTER :: xas_atom_env
251 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
252 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
253 :
254 48 : NULLIFY (xas_tdp_env, xas_tdp_control, atomic_kind_set, atoms_of_kind, current_state)
255 48 : NULLIFY (xas_atom_env, dft_control, matrix_ks, admm_env, qs_kind_set, tmp_basis)
256 :
257 : ! Initialization
258 96 : output_unit = cp_logger_get_default_io_unit()
259 :
260 48 : IF (output_unit > 0) THEN
261 : WRITE (UNIT=output_unit, FMT="(/,T3,A)") &
262 24 : "# Create and initialize the XAS_TDP environment"
263 : END IF
264 48 : CALL get_qs_env(qs_env, dft_control=dft_control)
265 48 : CALL xas_tdp_init(xas_tdp_env, xas_tdp_control, qs_env)
266 48 : CALL print_info(output_unit, xas_tdp_control, qs_env)
267 :
268 48 : IF (output_unit > 0) THEN
269 24 : IF (xas_tdp_control%check_only) THEN
270 0 : CPWARN("This is a CHECK_ONLY run for donor MOs verification")
271 : END IF
272 : END IF
273 :
274 : ! Localization of the core orbitals if requested (used for better identification of donor states)
275 48 : IF (xas_tdp_control%do_loc) THEN
276 32 : IF (output_unit > 0) THEN
277 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/)") &
278 16 : "# Localizing core orbitals for better identification"
279 : END IF
280 : ! closed shell or ROKS => myspin=1
281 32 : IF (xas_tdp_control%do_uks) THEN
282 6 : DO ispin = 1, dft_control%nspins
283 : CALL qs_loc_driver(qs_env, xas_tdp_env%qs_loc_env, &
284 6 : xas_tdp_control%print_loc_subsection, myspin=ispin)
285 : END DO
286 : ELSE
287 : CALL qs_loc_driver(qs_env, xas_tdp_env%qs_loc_env, &
288 30 : xas_tdp_control%print_loc_subsection, myspin=1)
289 : END IF
290 : END IF
291 :
292 : ! Find the MO centers
293 48 : CALL find_mo_centers(xas_tdp_env, xas_tdp_control, qs_env)
294 :
295 : ! Assign lowest energy orbitals to excited atoms
296 48 : CALL assign_mos_to_ex_atoms(xas_tdp_env, xas_tdp_control, qs_env)
297 :
298 : ! Once assigned, diagonalize the MOs wrt the KS matrix in the subspace associated to each atom
299 48 : IF (xas_tdp_control%do_loc) THEN
300 32 : IF (output_unit > 0) THEN
301 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/,T5,A)") &
302 16 : "# Diagonalize localized MOs wrt the KS matrix in the subspace of each excited", &
303 32 : "atom for better donor state identification."
304 : END IF
305 32 : CALL diagonalize_assigned_mo_subset(xas_tdp_env, xas_tdp_control, qs_env)
306 : ! update MO centers
307 32 : CALL find_mo_centers(xas_tdp_env, xas_tdp_control, qs_env)
308 : END IF
309 :
310 48 : IF (output_unit > 0) THEN
311 : WRITE (UNIT=output_unit, FMT="(/,T3,A,I4,A,/)") &
312 24 : "# Assign the relevant subset of the ", xas_tdp_control%n_search, &
313 48 : " lowest energy MOs to excited atoms"
314 : END IF
315 48 : CALL write_mos_to_ex_atoms_association(xas_tdp_env, xas_tdp_control, qs_env)
316 :
317 : ! If CHECK_ONLY run, check the donor MOs
318 48 : IF (xas_tdp_control%check_only) CALL print_checks(xas_tdp_env, xas_tdp_control, qs_env)
319 :
320 : ! If not simply exact exchange, setup a xas_atom_env and compute the xc integrals on the atomic grids
321 : ! Also needed if SOC is included or XPS GW2X(). Done before looping on atoms as it's all done at once
322 : IF ((xas_tdp_control%do_xc .OR. xas_tdp_control%do_soc .OR. xas_tdp_control%do_gw2x) &
323 48 : .AND. .NOT. xas_tdp_control%check_only) THEN
324 :
325 48 : IF (output_unit > 0 .AND. xas_tdp_control%do_xc) THEN
326 : WRITE (UNIT=output_unit, FMT="(/,T3,A,I4,A)") &
327 19 : "# Integrating the xc kernel on the atomic grids ..."
328 19 : CALL m_flush(output_unit)
329 : END IF
330 :
331 48 : CALL xas_atom_env_create(xas_atom_env)
332 48 : CALL init_xas_atom_env(xas_atom_env, xas_tdp_env, xas_tdp_control, qs_env)
333 48 : do_os = xas_tdp_control%do_uks .OR. xas_tdp_control%do_roks
334 :
335 48 : IF (xas_tdp_control%do_xc .AND. (.NOT. xas_tdp_control%xps_only)) THEN
336 38 : CALL integrate_fxc_atoms(xas_tdp_env%ri_fxc, xas_atom_env, xas_tdp_control, qs_env)
337 : END IF
338 :
339 48 : IF (xas_tdp_control%do_soc .OR. xas_tdp_control%do_gw2x) THEN
340 22 : CALL integrate_soc_atoms(xas_tdp_env%orb_soc, xas_atom_env=xas_atom_env, qs_env=qs_env)
341 : END IF
342 :
343 48 : CALL xas_atom_env_release(xas_atom_env)
344 : END IF
345 :
346 : ! Compute the 3-center Coulomb integrals for the whole system
347 48 : IF ((.NOT. (xas_tdp_control%check_only .OR. xas_tdp_control%xps_only)) .AND. &
348 : (xas_tdp_control%do_xc .OR. xas_tdp_control%do_coulomb)) THEN
349 44 : IF (output_unit > 0) THEN
350 : WRITE (UNIT=output_unit, FMT="(/,T3,A,I4,A)") &
351 22 : "# Computing the RI 3-center Coulomb integrals ..."
352 22 : CALL m_flush(output_unit)
353 : END IF
354 44 : CALL compute_ri_3c_coulomb(xas_tdp_env, qs_env)
355 :
356 : END IF
357 :
358 : ! Loop over donor states for calculation
359 48 : CALL get_qs_env(qs_env=qs_env, atomic_kind_set=atomic_kind_set)
360 48 : current_state_index = 1
361 :
362 : ! Loop over atomic kinds
363 122 : DO ikind = 1, SIZE(atomic_kind_set)
364 :
365 74 : IF (xas_tdp_control%check_only) EXIT
366 102 : IF (.NOT. ANY(xas_tdp_env%ex_kind_indices == ikind)) CYCLE
367 :
368 : CALL get_atomic_kind(atomic_kind=atomic_kind_set(ikind), name=kind_name, &
369 52 : atom_list=atoms_of_kind)
370 :
371 : ! compute the RI coulomb2 inverse for this kind, and RI exchange2 if needed
372 52 : CALL compute_ri_coulomb2_int(ikind, xas_tdp_env, xas_tdp_control, qs_env)
373 52 : IF (xas_tdp_control%do_hfx) THEN
374 42 : CALL compute_ri_exchange2_int(ikind, xas_tdp_env, xas_tdp_control, qs_env)
375 : END IF
376 :
377 : !Randomly distribute excited atoms of current kinds into batches for optimal load balance
378 : !of RI 3c exchange integrals. Take batch sizes of 2 to avoid taxing memory too much, while
379 : !greatly improving load balance
380 52 : batch_size = 2
381 52 : CALL get_ri_3c_batches(ex_atoms_of_kind, nbatch, batch_size, atoms_of_kind, xas_tdp_env)
382 52 : nex_atom = SIZE(ex_atoms_of_kind)
383 :
384 : !Loop over batches
385 104 : DO ibatch = 1, nbatch
386 :
387 52 : bo = get_limit(nex_atom, nbatch, ibatch - 1)
388 52 : batch_size = bo(2) - bo(1) + 1
389 156 : ALLOCATE (batch_atoms(batch_size))
390 52 : iatom = 0
391 110 : DO iat = bo(1), bo(2)
392 58 : iatom = iatom + 1
393 110 : batch_atoms(iatom) = ex_atoms_of_kind(iat)
394 : END DO
395 52 : CALL sort_unique(batch_atoms, unique)
396 :
397 : !compute RI 3c exchange integrals on batch, if so required
398 52 : IF (xas_tdp_control%do_hfx) THEN
399 42 : IF (output_unit > 0) THEN
400 : WRITE (UNIT=output_unit, FMT="(/,T3,A,I4,A,I4,A,I1,A,A)") &
401 21 : "# Computing the RI 3-center Exchange integrals for batch ", ibatch, "(/", nbatch, ") of ", &
402 42 : batch_size, " atoms of kind: ", TRIM(kind_name)
403 21 : CALL m_flush(output_unit)
404 : END IF
405 42 : CALL compute_ri_3c_exchange(batch_atoms, xas_tdp_env, xas_tdp_control, qs_env)
406 : END IF
407 :
408 : ! Loop over atoms of batch
409 110 : DO iat = 1, batch_size
410 58 : iatom = batch_atoms(iat)
411 :
412 58 : tmp_index = locate(xas_tdp_env%ex_atom_indices, iatom)
413 :
414 : !if dipole in length rep, compute the dipole in the AO basis for this atom
415 : !if quadrupole is required, compute it there too (in length rep)
416 58 : IF (xas_tdp_control%dipole_form == xas_dip_len .OR. xas_tdp_control%do_quad) THEN
417 24 : CALL compute_lenrep_multipole(iatom, xas_tdp_env, xas_tdp_control, qs_env)
418 : END IF
419 :
420 : ! Loop over states of excited atom of kind
421 126 : DO istate = 1, SIZE(xas_tdp_env%state_types, 1)
422 :
423 68 : IF (xas_tdp_env%state_types(istate, tmp_index) == xas_not_excited) CYCLE
424 :
425 68 : current_state => xas_tdp_env%donor_states(current_state_index)
426 : CALL set_donor_state(current_state, at_index=iatom, &
427 : at_symbol=kind_name, kind_index=ikind, &
428 68 : state_type=xas_tdp_env%state_types(istate, tmp_index))
429 :
430 : ! Initial write for the donor state of interest
431 68 : IF (output_unit > 0) THEN
432 : WRITE (UNIT=output_unit, FMT="(/,T3,A,A2,A,I4,A,A,/)") &
433 34 : "# Start of calculations for donor state of type ", &
434 34 : xas_tdp_env%state_type_char(current_state%state_type), " for atom", &
435 68 : current_state%at_index, " of kind ", TRIM(current_state%at_symbol)
436 34 : CALL m_flush(output_unit)
437 : END IF
438 :
439 : ! Assign best fitting MO(s) to current core donnor state
440 68 : CALL assign_mos_to_donor_state(current_state, xas_tdp_env, xas_tdp_control, qs_env)
441 :
442 : ! Perform MO restricted Mulliken pop analysis for verification
443 68 : CALL perform_mulliken_on_donor_state(current_state, qs_env)
444 :
445 : ! GW2X correction
446 68 : IF (xas_tdp_control%do_gw2x) THEN
447 30 : CALL GW2X_shift(current_state, xas_tdp_env, xas_tdp_control, qs_env)
448 : END IF
449 :
450 : ! Do main XAS calculations here
451 68 : IF (.NOT. xas_tdp_control%xps_only) THEN
452 56 : CALL setup_xas_tdp_prob(current_state, qs_env, xas_tdp_env, xas_tdp_control)
453 :
454 56 : IF (xas_tdp_control%do_spin_cons) THEN
455 : CALL solve_xas_tdp_prob(current_state, xas_tdp_control, xas_tdp_env, qs_env, &
456 8 : ex_type=tddfpt_spin_cons)
457 8 : CALL compute_dipole_fosc(current_state, xas_tdp_control, xas_tdp_env)
458 8 : IF (xas_tdp_control%do_quad) CALL compute_quadrupole_fosc(current_state, &
459 0 : xas_tdp_control, xas_tdp_env)
460 : CALL xas_tdp_post(tddfpt_spin_cons, current_state, xas_tdp_env, &
461 8 : xas_tdp_section, qs_env)
462 8 : CALL write_donor_state_restart(tddfpt_spin_cons, current_state, xas_tdp_section, qs_env)
463 : END IF
464 :
465 56 : IF (xas_tdp_control%do_spin_flip) THEN
466 : CALL solve_xas_tdp_prob(current_state, xas_tdp_control, xas_tdp_env, qs_env, &
467 2 : ex_type=tddfpt_spin_flip)
468 : !no dipole in spin-flip (spin-forbidden)
469 : CALL xas_tdp_post(tddfpt_spin_flip, current_state, xas_tdp_env, &
470 2 : xas_tdp_section, qs_env)
471 2 : CALL write_donor_state_restart(tddfpt_spin_flip, current_state, xas_tdp_section, qs_env)
472 : END IF
473 :
474 56 : IF (xas_tdp_control%do_singlet) THEN
475 : CALL solve_xas_tdp_prob(current_state, xas_tdp_control, xas_tdp_env, qs_env, &
476 48 : ex_type=tddfpt_singlet)
477 48 : CALL compute_dipole_fosc(current_state, xas_tdp_control, xas_tdp_env)
478 48 : IF (xas_tdp_control%do_quad) CALL compute_quadrupole_fosc(current_state, &
479 0 : xas_tdp_control, xas_tdp_env)
480 : CALL xas_tdp_post(tddfpt_singlet, current_state, xas_tdp_env, &
481 48 : xas_tdp_section, qs_env)
482 48 : CALL write_donor_state_restart(tddfpt_singlet, current_state, xas_tdp_section, qs_env)
483 : END IF
484 :
485 56 : IF (xas_tdp_control%do_triplet) THEN
486 : CALL solve_xas_tdp_prob(current_state, xas_tdp_control, xas_tdp_env, qs_env, &
487 2 : ex_type=tddfpt_triplet)
488 : !no dipole for triplets by construction
489 : CALL xas_tdp_post(tddfpt_triplet, current_state, xas_tdp_env, &
490 2 : xas_tdp_section, qs_env)
491 2 : CALL write_donor_state_restart(tddfpt_triplet, current_state, xas_tdp_section, qs_env)
492 : END IF
493 :
494 : ! Include the SOC if required, only for 2p donor stataes
495 56 : IF (xas_tdp_control%do_soc .AND. current_state%state_type == xas_2p_type) THEN
496 4 : IF (xas_tdp_control%do_singlet .AND. xas_tdp_control%do_triplet) THEN
497 2 : CALL include_rcs_soc(current_state, xas_tdp_env, xas_tdp_control, qs_env)
498 : END IF
499 4 : IF (xas_tdp_control%do_spin_cons .AND. xas_tdp_control%do_spin_flip) THEN
500 2 : CALL include_os_soc(current_state, xas_tdp_env, xas_tdp_control, qs_env)
501 : END IF
502 : END IF
503 :
504 : ! Print the requested properties
505 56 : CALL print_xas_tdp_to_file(current_state, xas_tdp_env, xas_tdp_control, xas_tdp_section)
506 : END IF !xps_only
507 68 : IF (xas_tdp_control%do_gw2x) CALL print_xps(current_state, xas_tdp_env, xas_tdp_control, qs_env)
508 :
509 : ! Free some unneeded attributes of current_state
510 68 : CALL free_ds_memory(current_state)
511 :
512 68 : current_state_index = current_state_index + 1
513 126 : NULLIFY (current_state)
514 :
515 : END DO ! state type
516 :
517 58 : end_of_batch = .FALSE.
518 58 : IF (iat == batch_size) end_of_batch = .TRUE.
519 110 : CALL free_exat_memory(xas_tdp_env, iatom, end_of_batch)
520 : END DO ! atom of batch
521 156 : DEALLOCATE (batch_atoms)
522 : END DO !ibatch
523 174 : DEALLOCATE (ex_atoms_of_kind)
524 : END DO ! kind
525 :
526 : ! Return to ususal KS matrix
527 48 : IF (dft_control%do_admm) THEN
528 4 : CALL get_qs_env(qs_env, matrix_ks=matrix_ks, admm_env=admm_env)
529 8 : DO ispin = 1, dft_control%nspins
530 8 : CALL admm_uncorrect_for_eigenvalues(ispin, admm_env, matrix_ks(ispin)%matrix)
531 : END DO
532 : END IF
533 :
534 : ! Return to initial basis set radii
535 48 : IF (xas_tdp_control%eps_pgf > 0.0_dp) THEN
536 0 : CALL get_qs_env(qs_env, qs_kind_set=qs_kind_set)
537 0 : DO ikind = 1, SIZE(atomic_kind_set)
538 0 : CALL get_qs_kind(qs_kind_set(ikind), basis_set=tmp_basis, basis_type="ORB")
539 0 : CALL init_interaction_radii_orb_basis(tmp_basis, eps_pgf_orb=dft_control%qs_control%eps_pgf_orb)
540 : END DO
541 : END IF
542 :
543 : ! Clean-up
544 48 : CALL xas_tdp_env_release(xas_tdp_env)
545 48 : CALL xas_tdp_control_release(xas_tdp_control)
546 :
547 96 : END SUBROUTINE xas_tdp_core
548 :
549 : ! **************************************************************************************************
550 : !> \brief Overall control and environment types initialization
551 : !> \param xas_tdp_env the environment type to initialize
552 : !> \param xas_tdp_control the control type to initialize
553 : !> \param qs_env the inherited qs environement type
554 : ! **************************************************************************************************
555 48 : SUBROUTINE xas_tdp_init(xas_tdp_env, xas_tdp_control, qs_env)
556 :
557 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
558 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
559 : TYPE(qs_environment_type), POINTER :: qs_env
560 :
561 : CHARACTER(LEN=default_string_length) :: kind_name
562 : INTEGER :: at_ind, i, ispin, j, k, kind_ind, &
563 : n_donor_states, n_kinds, nao, &
564 : nat_of_kind, natom, nex_atoms, &
565 : nex_kinds, nmatch, nspins
566 : INTEGER, DIMENSION(2) :: homo, n_mo, n_moloc
567 48 : INTEGER, DIMENSION(:), POINTER :: ind_of_kind
568 : LOGICAL :: do_os, do_uks, unique
569 : REAL(dp) :: fact
570 48 : REAL(dp), DIMENSION(:), POINTER :: mo_evals
571 : TYPE(admm_type), POINTER :: admm_env
572 48 : TYPE(atomic_kind_type), DIMENSION(:), POINTER :: at_kind_set
573 : TYPE(cell_type), POINTER :: cell
574 : TYPE(cp_fm_type), POINTER :: mo_coeff
575 48 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks, matrix_s, rho_ao
576 : TYPE(dbcsr_type) :: matrix_tmp
577 : TYPE(dft_control_type), POINTER :: dft_control
578 : TYPE(gto_basis_set_type), POINTER :: tmp_basis
579 48 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
580 48 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
581 48 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
582 : TYPE(qs_loc_env_type), POINTER :: qs_loc_env
583 : TYPE(qs_rho_type), POINTER :: rho
584 : TYPE(section_type), POINTER :: dummy_section
585 : TYPE(section_vals_type), POINTER :: loc_section, xas_tdp_section
586 :
587 48 : NULLIFY (xas_tdp_section, at_kind_set, ind_of_kind, dft_control, qs_kind_set, tmp_basis)
588 48 : NULLIFY (qs_loc_env, loc_section, mos, particle_set, rho, rho_ao, mo_evals, cell)
589 48 : NULLIFY (mo_coeff, matrix_ks, admm_env, dummy_section)
590 :
591 : ! XAS TDP control type initialization
592 96 : xas_tdp_section => section_vals_get_subs_vals(qs_env%input, "DFT%XAS_TDP")
593 :
594 48 : CALL get_qs_env(qs_env, dft_control=dft_control)
595 48 : CALL xas_tdp_control_create(xas_tdp_control)
596 48 : CALL read_xas_tdp_control(xas_tdp_control, xas_tdp_section)
597 :
598 : ! Check the qs_env for a LSD/ROKS calculation
599 48 : IF (dft_control%uks) xas_tdp_control%do_uks = .TRUE.
600 48 : IF (dft_control%roks) xas_tdp_control%do_roks = .TRUE.
601 48 : do_uks = xas_tdp_control%do_uks
602 48 : do_os = do_uks .OR. xas_tdp_control%do_roks
603 :
604 : ! XAS TDP environment type initialization
605 48 : CALL xas_tdp_env_create(xas_tdp_env)
606 :
607 : ! Retrieving the excited atoms indices and correspondig state types
608 48 : IF (xas_tdp_control%define_excited == xas_tdp_by_index) THEN
609 :
610 : ! simply copy indices from xas_tdp_control
611 26 : nex_atoms = SIZE(xas_tdp_control%list_ex_atoms)
612 26 : CALL set_xas_tdp_env(xas_tdp_env, nex_atoms=nex_atoms)
613 78 : ALLOCATE (xas_tdp_env%ex_atom_indices(nex_atoms))
614 104 : ALLOCATE (xas_tdp_env%state_types(SIZE(xas_tdp_control%state_types, 1), nex_atoms))
615 86 : xas_tdp_env%ex_atom_indices = xas_tdp_control%list_ex_atoms
616 146 : xas_tdp_env%state_types = xas_tdp_control%state_types
617 :
618 : ! Test that these indices are within the range of available atoms
619 26 : CALL get_qs_env(qs_env=qs_env, natom=natom)
620 56 : IF (ANY(xas_tdp_env%ex_atom_indices > natom)) THEN
621 0 : CPABORT("Invalid index for the ATOM_LIST keyword.")
622 : END IF
623 :
624 : ! Check atom kinds and fill corresponding array
625 78 : ALLOCATE (xas_tdp_env%ex_kind_indices(nex_atoms))
626 56 : xas_tdp_env%ex_kind_indices = 0
627 26 : k = 0
628 26 : CALL get_qs_env(qs_env, particle_set=particle_set)
629 56 : DO i = 1, nex_atoms
630 30 : at_ind = xas_tdp_env%ex_atom_indices(i)
631 30 : CALL get_atomic_kind(particle_set(at_ind)%atomic_kind, kind_number=j)
632 90 : IF (ALL(ABS(xas_tdp_env%ex_kind_indices - j) .NE. 0)) THEN
633 28 : k = k + 1
634 28 : xas_tdp_env%ex_kind_indices(k) = j
635 : END IF
636 : END DO
637 26 : nex_kinds = k
638 26 : CALL set_xas_tdp_env(xas_tdp_env, nex_kinds=nex_kinds)
639 26 : CALL reallocate(xas_tdp_env%ex_kind_indices, 1, nex_kinds)
640 :
641 22 : ELSE IF (xas_tdp_control%define_excited == xas_tdp_by_kind) THEN
642 :
643 : ! need to find out which atom of which kind is excited
644 22 : CALL get_qs_env(qs_env=qs_env, atomic_kind_set=at_kind_set)
645 22 : n_kinds = SIZE(at_kind_set)
646 22 : nex_atoms = 0
647 :
648 22 : nex_kinds = SIZE(xas_tdp_control%list_ex_kinds)
649 66 : ALLOCATE (xas_tdp_env%ex_kind_indices(nex_kinds))
650 22 : k = 0
651 :
652 66 : DO i = 1, n_kinds
653 : CALL get_atomic_kind(atomic_kind=at_kind_set(i), name=kind_name, &
654 44 : natom=nat_of_kind, kind_number=kind_ind)
655 90 : IF (ANY(xas_tdp_control%list_ex_kinds == kind_name)) THEN
656 24 : nex_atoms = nex_atoms + nat_of_kind
657 24 : k = k + 1
658 24 : xas_tdp_env%ex_kind_indices(k) = kind_ind
659 : END IF
660 : END DO
661 :
662 66 : ALLOCATE (xas_tdp_env%ex_atom_indices(nex_atoms))
663 88 : ALLOCATE (xas_tdp_env%state_types(SIZE(xas_tdp_control%state_types, 1), nex_atoms))
664 22 : nex_atoms = 0
665 22 : nmatch = 0
666 :
667 66 : DO i = 1, n_kinds
668 : CALL get_atomic_kind(atomic_kind=at_kind_set(i), name=kind_name, &
669 44 : natom=nat_of_kind, atom_list=ind_of_kind)
670 116 : DO j = 1, nex_kinds
671 94 : IF (xas_tdp_control%list_ex_kinds(j) == kind_name) THEN
672 80 : xas_tdp_env%ex_atom_indices(nex_atoms + 1:nex_atoms + nat_of_kind) = ind_of_kind
673 58 : DO k = 1, SIZE(xas_tdp_control%state_types, 1)
674 : xas_tdp_env%state_types(k, nex_atoms + 1:nex_atoms + nat_of_kind) = &
675 96 : xas_tdp_control%state_types(k, j)
676 : END DO
677 24 : nex_atoms = nex_atoms + nat_of_kind
678 24 : nmatch = nmatch + 1
679 : END IF
680 : END DO
681 : END DO
682 :
683 22 : CALL set_xas_tdp_env(xas_tdp_env, nex_atoms=nex_atoms, nex_kinds=nex_kinds)
684 :
685 : ! Verifying that the input was valid
686 22 : IF (nmatch .NE. SIZE(xas_tdp_control%list_ex_kinds)) THEN
687 0 : CPABORT("Invalid kind(s) for the KIND_LIST keyword.")
688 : END IF
689 :
690 : END IF
691 :
692 : ! Sort the excited atoms indices (for convinience and use of locate function)
693 48 : CALL sort_unique(xas_tdp_env%ex_atom_indices, unique)
694 48 : IF (.NOT. unique) THEN
695 0 : CPABORT("Excited atoms not uniquely defined.")
696 : END IF
697 :
698 : ! Check for periodicity
699 48 : CALL get_qs_env(qs_env, cell=cell)
700 144 : IF (ALL(cell%perd == 0)) THEN
701 32 : xas_tdp_control%is_periodic = .FALSE.
702 64 : ELSE IF (ALL(cell%perd == 1)) THEN
703 16 : xas_tdp_control%is_periodic = .TRUE.
704 : ELSE
705 0 : CPABORT("XAS TDP only implemented for full PBCs or non-PBCs")
706 : END IF
707 :
708 : ! Allocating memory for the array of donor states
709 174 : n_donor_states = COUNT(xas_tdp_env%state_types /= xas_not_excited)
710 212 : ALLOCATE (xas_tdp_env%donor_states(n_donor_states))
711 116 : DO i = 1, n_donor_states
712 116 : CALL donor_state_create(xas_tdp_env%donor_states(i))
713 : END DO
714 :
715 : ! In case of ADMM, for the whole duration of the XAS_TDP, we need the total KS matrix
716 48 : IF (dft_control%do_admm) THEN
717 4 : CALL get_qs_env(qs_env, admm_env=admm_env, matrix_ks=matrix_ks)
718 :
719 8 : DO ispin = 1, dft_control%nspins
720 8 : CALL admm_correct_for_eigenvalues(ispin, admm_env, matrix_ks(ispin)%matrix)
721 : END DO
722 : END IF
723 :
724 : ! In case of externally imposed EPS_PGF_XAS, need to update ORB and RI_XAS interaction radii
725 48 : IF (xas_tdp_control%eps_pgf > 0.0_dp) THEN
726 0 : CALL get_qs_env(qs_env, qs_kind_set=qs_kind_set)
727 :
728 0 : DO i = 1, SIZE(qs_kind_set)
729 0 : CALL get_qs_kind(qs_kind_set(i), basis_set=tmp_basis, basis_type="ORB")
730 0 : CALL init_interaction_radii_orb_basis(tmp_basis, eps_pgf_orb=xas_tdp_control%eps_pgf)
731 0 : CALL get_qs_kind(qs_kind_set(i), basis_set=tmp_basis, basis_type="RI_XAS")
732 0 : CALL init_interaction_radii_orb_basis(tmp_basis, eps_pgf_orb=xas_tdp_control%eps_pgf)
733 : END DO
734 : END IF
735 :
736 : ! In case of ground state OT optimization, compute the MO eigenvalues and get canonical MOs
737 48 : IF (qs_env%scf_env%method == ot_method_nr) THEN
738 :
739 4 : CALL get_qs_env(qs_env, mos=mos, matrix_ks=matrix_ks)
740 4 : nspins = 1; IF (do_uks) nspins = 2
741 :
742 8 : DO ispin = 1, nspins
743 4 : CALL get_mo_set(mos(ispin), mo_coeff=mo_coeff, eigenvalues=mo_evals)
744 8 : CALL calculate_subspace_eigenvalues(mo_coeff, matrix_ks(ispin)%matrix, evals_arg=mo_evals)
745 : END DO
746 : END IF
747 :
748 : ! Initializing the qs_loc_env from the LOCALIZE subsection of XAS_TDP (largely inpired by MI's XAS)
749 : ! We create the LOCALIZE subsection here, since it is completely overwritten anyways
750 48 : CALL create_localize_section(dummy_section)
751 48 : CALL section_vals_create(xas_tdp_control%loc_subsection, dummy_section)
752 : CALL section_vals_val_set(xas_tdp_control%loc_subsection, "_SECTION_PARAMETERS_", &
753 48 : l_val=xas_tdp_control%do_loc)
754 48 : CALL section_release(dummy_section)
755 : xas_tdp_control%print_loc_subsection => section_vals_get_subs_vals( &
756 48 : xas_tdp_control%loc_subsection, "PRINT")
757 :
758 48 : ALLOCATE (xas_tdp_env%qs_loc_env)
759 48 : CALL qs_loc_env_create(xas_tdp_env%qs_loc_env)
760 48 : qs_loc_env => xas_tdp_env%qs_loc_env
761 48 : loc_section => xas_tdp_control%loc_subsection
762 : ! getting the number of MOs
763 48 : CALL get_qs_env(qs_env, mos=mos)
764 48 : CALL get_mo_set(mos(1), nmo=n_mo(1), homo=homo(1), nao=nao)
765 48 : n_mo(2) = n_mo(1)
766 48 : homo(2) = homo(1)
767 48 : nspins = 1
768 48 : IF (do_os) CALL get_mo_set(mos(2), nmo=n_mo(2), homo=homo(2))
769 48 : IF (do_uks) nspins = 2 !in roks, same MOs for both spins
770 :
771 : ! by default, all (doubly occupied) homo are localized
772 144 : IF (xas_tdp_control%n_search < 0 .OR. xas_tdp_control%n_search > MINVAL(homo)) &
773 0 : xas_tdp_control%n_search = MINVAL(homo)
774 : CALL qs_loc_control_init(qs_loc_env, loc_section, do_homo=.TRUE., do_xas=.TRUE., &
775 48 : nloc_xas=xas_tdp_control%n_search, spin_xas=1)
776 :
777 : ! do_xas argument above only prepares spin-alpha localization
778 48 : IF (do_uks) THEN
779 6 : qs_loc_env%localized_wfn_control%nloc_states(2) = xas_tdp_control%n_search
780 6 : qs_loc_env%localized_wfn_control%lu_bound_states(1, 2) = 1
781 6 : qs_loc_env%localized_wfn_control%lu_bound_states(2, 2) = xas_tdp_control%n_search
782 : END IF
783 :
784 : ! final qs_loc_env initialization. Impose Berry operator
785 48 : qs_loc_env%localized_wfn_control%operator_type = op_loc_berry
786 48 : qs_loc_env%localized_wfn_control%max_iter = 25000
787 48 : IF (.NOT. xas_tdp_control%do_loc) THEN
788 16 : qs_loc_env%localized_wfn_control%localization_method = do_loc_none
789 : ELSE
790 96 : n_moloc = qs_loc_env%localized_wfn_control%nloc_states
791 32 : CALL set_loc_centers(qs_loc_env%localized_wfn_control, n_moloc, nspins)
792 32 : IF (do_uks) THEN
793 : CALL qs_loc_env_init(qs_loc_env, qs_loc_env%localized_wfn_control, &
794 2 : qs_env, do_localize=.TRUE.)
795 : ELSE
796 : CALL qs_loc_env_init(qs_loc_env, qs_loc_env%localized_wfn_control, &
797 30 : qs_env, do_localize=.TRUE., myspin=1)
798 : END IF
799 : END IF
800 :
801 : ! Allocating memory for the array of excited atoms MOs. Worst case senario, all searched MOs are
802 : ! associated to the same atom
803 240 : ALLOCATE (xas_tdp_env%mos_of_ex_atoms(xas_tdp_control%n_search, nex_atoms, nspins))
804 :
805 : ! Compute the projector on the unoccupied, unperturbed ground state: Q = 1 - SP, sor each spin
806 48 : IF (do_os) nspins = 2
807 48 : CALL get_qs_env(qs_env, rho=rho, matrix_s=matrix_s)
808 48 : CALL qs_rho_get(rho, rho_ao=rho_ao)
809 :
810 198 : ALLOCATE (xas_tdp_env%q_projector(nspins))
811 48 : ALLOCATE (xas_tdp_env%q_projector(1)%matrix)
812 : CALL dbcsr_create(xas_tdp_env%q_projector(1)%matrix, name="Q PROJECTOR ALPHA", &
813 48 : template=matrix_s(1)%matrix, matrix_type=dbcsr_type_no_symmetry)
814 48 : IF (do_os) THEN
815 6 : ALLOCATE (xas_tdp_env%q_projector(2)%matrix)
816 : CALL dbcsr_create(xas_tdp_env%q_projector(2)%matrix, name="Q PROJECTOR BETA", &
817 6 : template=matrix_s(1)%matrix, matrix_type=dbcsr_type_no_symmetry)
818 : END IF
819 :
820 : ! In the case of spin-restricted calculations, rho_ao includes double occupency => 0.5 prefactor
821 48 : fact = -0.5_dp; IF (do_os) fact = -1.0_dp
822 : CALL dbcsr_multiply('N', 'N', fact, matrix_s(1)%matrix, rho_ao(1)%matrix, 0.0_dp, &
823 48 : xas_tdp_env%q_projector(1)%matrix, filter_eps=xas_tdp_control%eps_filter)
824 48 : CALL dbcsr_add_on_diag(xas_tdp_env%q_projector(1)%matrix, 1.0_dp)
825 48 : CALL dbcsr_finalize(xas_tdp_env%q_projector(1)%matrix)
826 :
827 48 : IF (do_os) THEN
828 : CALL dbcsr_multiply('N', 'N', fact, matrix_s(1)%matrix, rho_ao(2)%matrix, 0.0_dp, &
829 6 : xas_tdp_env%q_projector(2)%matrix, filter_eps=xas_tdp_control%eps_filter)
830 6 : CALL dbcsr_add_on_diag(xas_tdp_env%q_projector(2)%matrix, 1.0_dp)
831 6 : CALL dbcsr_finalize(xas_tdp_env%q_projector(2)%matrix)
832 : END IF
833 :
834 : ! Create the structure for the dipole in the AO basis
835 192 : ALLOCATE (xas_tdp_env%dipmat(3))
836 192 : DO i = 1, 3
837 144 : ALLOCATE (xas_tdp_env%dipmat(i)%matrix)
838 144 : CALL dbcsr_copy(matrix_tmp, matrix_s(1)%matrix, name="XAS TDP dipole matrix")
839 144 : IF (xas_tdp_control%dipole_form == xas_dip_vel) THEN
840 : CALL dbcsr_create(xas_tdp_env%dipmat(i)%matrix, template=matrix_s(1)%matrix, &
841 90 : matrix_type=dbcsr_type_antisymmetric)
842 90 : CALL dbcsr_complete_redistribute(matrix_tmp, xas_tdp_env%dipmat(i)%matrix)
843 : ELSE
844 : CALL dbcsr_create(xas_tdp_env%dipmat(i)%matrix, template=matrix_s(1)%matrix, &
845 54 : matrix_type=dbcsr_type_symmetric)
846 54 : CALL dbcsr_copy(xas_tdp_env%dipmat(i)%matrix, matrix_tmp)
847 : END IF
848 144 : CALL dbcsr_set(xas_tdp_env%dipmat(i)%matrix, 0.0_dp)
849 192 : CALL dbcsr_release(matrix_tmp)
850 : END DO
851 :
852 : ! Create the structure for the electric quadrupole in the AO basis, if required
853 48 : IF (xas_tdp_control%do_quad) THEN
854 0 : ALLOCATE (xas_tdp_env%quadmat(6))
855 0 : DO i = 1, 6
856 0 : ALLOCATE (xas_tdp_env%quadmat(i)%matrix)
857 0 : CALL dbcsr_copy(xas_tdp_env%quadmat(i)%matrix, matrix_s(1)%matrix, name="XAS TDP quadrupole matrix")
858 0 : CALL dbcsr_set(xas_tdp_env%quadmat(i)%matrix, 0.0_dp)
859 : END DO
860 : END IF
861 :
862 : ! Precompute it in the velocity representation, if so chosen
863 48 : IF (xas_tdp_control%dipole_form == xas_dip_vel) THEN
864 : !enforce minimum image to avoid any PBCs related issues. Ok because very localized densities
865 30 : CALL p_xyz_ao(xas_tdp_env%dipmat, qs_env, minimum_image=.TRUE.)
866 : END IF
867 :
868 : ! Allocate SOC in AO basis matrices
869 48 : IF (xas_tdp_control%do_soc .OR. xas_tdp_control%do_gw2x) THEN
870 88 : ALLOCATE (xas_tdp_env%orb_soc(3))
871 88 : DO i = 1, 3
872 114 : ALLOCATE (xas_tdp_env%orb_soc(i)%matrix)
873 : END DO
874 : END IF
875 :
876 : ! Check that everything is allowed
877 48 : CALL safety_check(xas_tdp_control, qs_env)
878 :
879 : ! Initialize libint for the 3-center integrals
880 48 : CALL cp_libint_static_init()
881 :
882 : ! Compute LUMOs as guess for OT solver and/or for GW2X correction
883 48 : IF (xas_tdp_control%do_ot .OR. xas_tdp_control%do_gw2x) THEN
884 20 : CALL make_lumo_guess(xas_tdp_env, xas_tdp_control, qs_env)
885 : END IF
886 :
887 144 : END SUBROUTINE xas_tdp_init
888 :
889 : ! **************************************************************************************************
890 : !> \brief splits the excited atoms of a kind into batches for RI 3c integrals load balance
891 : !> \param ex_atoms_of_kind the excited atoms for the current kind, randomly shuffled
892 : !> \param nbatch number of batches to loop over
893 : !> \param batch_size standard size of a batch
894 : !> \param atoms_of_kind number of atoms for the current kind (excited or not)
895 : !> \param xas_tdp_env ...
896 : ! **************************************************************************************************
897 52 : SUBROUTINE get_ri_3c_batches(ex_atoms_of_kind, nbatch, batch_size, atoms_of_kind, xas_tdp_env)
898 :
899 : INTEGER, ALLOCATABLE, DIMENSION(:), INTENT(INOUT) :: ex_atoms_of_kind
900 : INTEGER, INTENT(OUT) :: nbatch
901 : INTEGER, INTENT(IN) :: batch_size
902 : INTEGER, DIMENSION(:), INTENT(IN) :: atoms_of_kind
903 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
904 :
905 : INTEGER :: iat, iatom, nex_atom
906 52 : TYPE(rng_stream_type), ALLOCATABLE :: rng_stream
907 :
908 : !Get the atoms from atoms_of_kind that are excited
909 52 : nex_atom = 0
910 268 : DO iat = 1, SIZE(atoms_of_kind)
911 216 : iatom = atoms_of_kind(iat)
912 444 : IF (.NOT. ANY(xas_tdp_env%ex_atom_indices == iatom)) CYCLE
913 268 : nex_atom = nex_atom + 1
914 : END DO
915 :
916 156 : ALLOCATE (ex_atoms_of_kind(nex_atom))
917 52 : nex_atom = 0
918 268 : DO iat = 1, SIZE(atoms_of_kind)
919 216 : iatom = atoms_of_kind(iat)
920 444 : IF (.NOT. ANY(xas_tdp_env%ex_atom_indices == iatom)) CYCLE
921 58 : nex_atom = nex_atom + 1
922 268 : ex_atoms_of_kind(nex_atom) = iatom
923 : END DO
924 :
925 : !We shuffle those atoms to spread them
926 52 : rng_stream = rng_stream_type(name="uniform_rng", distribution_type=UNIFORM)
927 52 : CALL rng_stream%shuffle(ex_atoms_of_kind(1:nex_atom))
928 :
929 52 : nbatch = nex_atom/batch_size
930 52 : IF (nbatch*batch_size .NE. nex_atom) nbatch = nbatch + 1
931 :
932 52 : END SUBROUTINE get_ri_3c_batches
933 :
934 : ! **************************************************************************************************
935 : !> \brief Checks for forbidden keywords combinations
936 : !> \param xas_tdp_control ...
937 : !> \param qs_env ...
938 : ! **************************************************************************************************
939 48 : SUBROUTINE safety_check(xas_tdp_control, qs_env)
940 :
941 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
942 : TYPE(qs_environment_type), POINTER :: qs_env
943 :
944 : TYPE(dft_control_type), POINTER :: dft_control
945 :
946 : !PB only available without exact exchange
947 : IF (xas_tdp_control%is_periodic .AND. xas_tdp_control%do_hfx &
948 48 : .AND. xas_tdp_control%x_potential%potential_type == do_potential_coulomb) THEN
949 0 : CPABORT("XAS TDP with Coulomb operator for exact exchange only supports non-periodic BCs")
950 : END IF
951 :
952 : !open-shell/closed-shell tests
953 48 : IF (xas_tdp_control%do_roks .OR. xas_tdp_control%do_uks) THEN
954 :
955 6 : IF (.NOT. (xas_tdp_control%do_spin_cons .OR. xas_tdp_control%do_spin_flip)) THEN
956 0 : CPABORT("Need spin-conserving and/or spin-flip excitations for open-shell systems")
957 : END IF
958 :
959 6 : IF (xas_tdp_control%do_singlet .OR. xas_tdp_control%do_triplet) THEN
960 0 : CPABORT("Singlet/triplet excitations only for restricted closed-shell systems")
961 : END IF
962 :
963 6 : IF (xas_tdp_control%do_soc .AND. .NOT. &
964 : (xas_tdp_control%do_spin_flip .AND. xas_tdp_control%do_spin_cons)) THEN
965 :
966 0 : CPABORT("Both spin-conserving and spin-flip excitations are required for SOC")
967 : END IF
968 : ELSE
969 :
970 42 : IF (.NOT. (xas_tdp_control%do_singlet .OR. xas_tdp_control%do_triplet)) THEN
971 0 : CPABORT("Need singlet and/or triplet excitations for closed-shell systems")
972 : END IF
973 :
974 42 : IF (xas_tdp_control%do_spin_cons .OR. xas_tdp_control%do_spin_flip) THEN
975 0 : CPABORT("Spin-conserving/spin-flip excitations only for open-shell systems")
976 : END IF
977 :
978 42 : IF (xas_tdp_control%do_soc .AND. .NOT. &
979 : (xas_tdp_control%do_singlet .AND. xas_tdp_control%do_triplet)) THEN
980 :
981 0 : CPABORT("Both singlet and triplet excitations are needed for SOC")
982 : END IF
983 : END IF
984 :
985 : !Warn against using E_RANGE with SOC
986 48 : IF (xas_tdp_control%do_soc .AND. xas_tdp_control%e_range > 0.0_dp) THEN
987 0 : CPWARN("Using E_RANGE and SOC together may lead to crashes, use N_EXCITED for safety.")
988 : END IF
989 :
990 : !TDA, full-TDDFT and diagonalization
991 48 : IF (.NOT. xas_tdp_control%tamm_dancoff) THEN
992 :
993 6 : IF (xas_tdp_control%do_spin_flip) THEN
994 0 : CPABORT("Spin-flip kernel only implemented for Tamm-Dancoff approximation")
995 : END IF
996 :
997 6 : IF (xas_tdp_control%do_ot) THEN
998 0 : CPABORT("OT diagonalization only available within the Tamm-Dancoff approximation")
999 : END IF
1000 : END IF
1001 :
1002 : !GW2X, need hfx kernel and LOCALIZE
1003 48 : IF (xas_tdp_control%do_gw2x) THEN
1004 18 : IF (.NOT. xas_tdp_control%do_hfx) THEN
1005 0 : CPABORT("GW2x requires the definition of the EXACT_EXCHANGE kernel")
1006 : END IF
1007 18 : IF (.NOT. xas_tdp_control%do_loc) THEN
1008 0 : CPABORT("GW2X requires the LOCALIZE keyword in DONOR_STATES")
1009 : END IF
1010 : END IF
1011 :
1012 : !Only allow ADMM schemes that correct for eigenvalues
1013 48 : CALL get_qs_env(qs_env, dft_control=dft_control)
1014 48 : IF (dft_control%do_admm) THEN
1015 : IF ((.NOT. qs_env%admm_env%purification_method == do_admm_purify_none) .AND. &
1016 4 : (.NOT. qs_env%admm_env%purification_method == do_admm_purify_cauchy_subspace) .AND. &
1017 : (.NOT. qs_env%admm_env%purification_method == do_admm_purify_mo_diag)) THEN
1018 :
1019 0 : CPABORT("XAS_TDP only compatible with ADMM purification NONE, CAUCHY_SUBSPACE and MO_DIAG")
1020 :
1021 : END IF
1022 : END IF
1023 :
1024 48 : END SUBROUTINE safety_check
1025 :
1026 : ! **************************************************************************************************
1027 : !> \brief Prints some basic info about the chosen parameters
1028 : !> \param ou the output unis
1029 : !> \param xas_tdp_control ...
1030 : !> \param qs_env ...
1031 : ! **************************************************************************************************
1032 48 : SUBROUTINE print_info(ou, xas_tdp_control, qs_env)
1033 :
1034 : INTEGER, INTENT(IN) :: ou
1035 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1036 : TYPE(qs_environment_type), POINTER :: qs_env
1037 :
1038 : INTEGER :: i
1039 : REAL(dp) :: occ
1040 48 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_s
1041 : TYPE(dft_control_type), POINTER :: dft_control
1042 : TYPE(section_vals_type), POINTER :: input, kernel_section
1043 :
1044 48 : NULLIFY (input, kernel_section, dft_control, matrix_s)
1045 :
1046 48 : CALL get_qs_env(qs_env, input=input, dft_control=dft_control, matrix_s=matrix_s)
1047 :
1048 : !Overlap matrix sparsity
1049 48 : occ = dbcsr_get_occupation(matrix_s(1)%matrix)
1050 :
1051 48 : IF (ou .LE. 0) RETURN
1052 :
1053 : !Reference calculation
1054 24 : IF (xas_tdp_control%do_uks) THEN
1055 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1056 3 : "XAS_TDP| Reference calculation: Unrestricted Kohn-Sham"
1057 21 : ELSE IF (xas_tdp_control%do_roks) THEN
1058 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1059 0 : "XAS_TDP| Reference calculation: Restricted Open-Shell Kohn-Sham"
1060 : ELSE
1061 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1062 21 : "XAS_TDP| Reference calculation: Restricted Closed-Shell Kohn-Sham"
1063 : END IF
1064 :
1065 : !TDA
1066 24 : IF (xas_tdp_control%tamm_dancoff) THEN
1067 : WRITE (UNIT=ou, FMT="(T3,A)") &
1068 21 : "XAS_TDP| Tamm-Dancoff Approximation (TDA): On"
1069 : ELSE
1070 : WRITE (UNIT=ou, FMT="(T3,A)") &
1071 3 : "XAS_TDP| Tamm-Dancoff Approximation (TDA): Off"
1072 : END IF
1073 :
1074 : !Dipole form
1075 24 : IF (xas_tdp_control%dipole_form == xas_dip_vel) THEN
1076 : WRITE (UNIT=ou, FMT="(T3,A)") &
1077 15 : "XAS_TDP| Transition Dipole Representation: VELOCITY"
1078 : ELSE
1079 : WRITE (UNIT=ou, FMT="(T3,A)") &
1080 9 : "XAS_TDP| Transition Dipole Representation: LENGTH"
1081 : END IF
1082 :
1083 : !Quadrupole
1084 24 : IF (xas_tdp_control%do_quad) THEN
1085 : WRITE (UNIT=ou, FMT="(T3,A)") &
1086 0 : "XAS_TDP| Transition Quadrupole: On"
1087 : END IF
1088 :
1089 : !EPS_PGF
1090 24 : IF (xas_tdp_control%eps_pgf > 0.0_dp) THEN
1091 : WRITE (UNIT=ou, FMT="(T3,A,ES7.1)") &
1092 0 : "XAS_TDP| EPS_PGF_XAS: ", xas_tdp_control%eps_pgf
1093 : ELSE
1094 : WRITE (UNIT=ou, FMT="(T3,A,ES7.1,A)") &
1095 24 : "XAS_TDP| EPS_PGF_XAS: ", dft_control%qs_control%eps_pgf_orb, " (= EPS_PGF_ORB)"
1096 : END IF
1097 :
1098 : !EPS_FILTER
1099 : WRITE (UNIT=ou, FMT="(T3,A,ES7.1)") &
1100 24 : "XAS_TDP| EPS_FILTER: ", xas_tdp_control%eps_filter
1101 :
1102 : !Grid info
1103 24 : IF (xas_tdp_control%do_xc) THEN
1104 : WRITE (UNIT=ou, FMT="(T3,A)") &
1105 19 : "XAS_TDP| Radial Grid(s) Info: Kind, na, nr"
1106 40 : DO i = 1, SIZE(xas_tdp_control%grid_info, 1)
1107 : WRITE (UNIT=ou, FMT="(T3,A,A6,A,A,A,A)") &
1108 21 : " ", TRIM(xas_tdp_control%grid_info(i, 1)), ", ", &
1109 61 : TRIM(xas_tdp_control%grid_info(i, 2)), ", ", TRIM(xas_tdp_control%grid_info(i, 3))
1110 : END DO
1111 : END IF
1112 :
1113 : !No kernel
1114 24 : IF (.NOT. xas_tdp_control%do_coulomb) THEN
1115 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1116 0 : "XAS_TDP| No kernel (standard DFT)"
1117 : END IF
1118 :
1119 : !XC kernel
1120 24 : IF (xas_tdp_control%do_xc) THEN
1121 :
1122 : WRITE (UNIT=ou, FMT="(/,T3,A,F5.2,A)") &
1123 19 : "XAS_TDP| RI Region's Radius: ", xas_tdp_control%ri_radius*angstrom, " Ang"
1124 :
1125 : WRITE (UNIT=ou, FMT="(T3,A,/)") &
1126 19 : "XAS_TDP| XC Kernel Functional(s) used for the kernel:"
1127 :
1128 19 : kernel_section => section_vals_get_subs_vals(input, "DFT%XAS_TDP%KERNEL")
1129 19 : CALL xc_write(ou, kernel_section, lsd=.TRUE.)
1130 : END IF
1131 :
1132 : !HFX kernel
1133 24 : IF (xas_tdp_control%do_hfx) THEN
1134 : WRITE (UNIT=ou, FMT="(/,T3,A,/,/,T3,A,F5.3)") &
1135 19 : "XAS_TDP| Exact Exchange Kernel: Yes ", &
1136 38 : "EXACT_EXCHANGE| Scale: ", xas_tdp_control%sx
1137 19 : IF (xas_tdp_control%x_potential%potential_type == do_potential_coulomb) THEN
1138 : WRITE (UNIT=ou, FMT="(T3,A)") &
1139 12 : "EXACT_EXCHANGE| Potential : Coulomb"
1140 7 : ELSE IF (xas_tdp_control%x_potential%potential_type == do_potential_truncated) THEN
1141 : WRITE (UNIT=ou, FMT="(T3,A,/,T3,A,F5.2,A,/,T3,A,A)") &
1142 3 : "EXACT_EXCHANGE| Potential: Truncated Coulomb", &
1143 3 : "EXACT_EXCHANGE| Range: ", xas_tdp_control%x_potential%cutoff_radius*angstrom, ", (Ang)", &
1144 6 : "EXACT_EXCHANGE| T_C_G_DATA: ", TRIM(xas_tdp_control%x_potential%filename)
1145 4 : ELSE IF (xas_tdp_control%x_potential%potential_type == do_potential_short) THEN
1146 : WRITE (UNIT=ou, FMT="(T3,A,/,T3,A,F5.2,A,/,T3,A,F5.2,A,/,T3,A,ES7.1)") &
1147 4 : "EXACT_EXCHANGE| Potential: Short Range", &
1148 4 : "EXACT_EXCHANGE| Omega: ", xas_tdp_control%x_potential%omega, ", (1/a0)", &
1149 4 : "EXACT_EXCHANGE| Effective Range: ", xas_tdp_control%x_potential%cutoff_radius*angstrom, ", (Ang)", &
1150 8 : "EXACT_EXCHANGE| EPS_RANGE: ", xas_tdp_control%eps_range
1151 : END IF
1152 19 : IF (xas_tdp_control%eps_screen > 1.0E-16) THEN
1153 : WRITE (UNIT=ou, FMT="(T3,A,ES7.1)") &
1154 19 : "EXACT_EXCHANGE| EPS_SCREENING: ", xas_tdp_control%eps_screen
1155 : END IF
1156 :
1157 : !RI metric
1158 19 : IF (xas_tdp_control%do_ri_metric) THEN
1159 :
1160 : WRITE (UNIT=ou, FMT="(/,T3,A)") &
1161 3 : "EXACT_EXCHANGE| Using a RI metric"
1162 3 : IF (xas_tdp_control%ri_m_potential%potential_type == do_potential_id) THEN
1163 : WRITE (UNIT=ou, FMT="(T3,A)") &
1164 1 : "EXACT_EXCHANGE RI_METRIC| Potential : Overlap"
1165 2 : ELSE IF (xas_tdp_control%ri_m_potential%potential_type == do_potential_truncated) THEN
1166 : WRITE (UNIT=ou, FMT="(T3,A,/,T3,A,F5.2,A,/,T3,A,A)") &
1167 1 : "EXACT_EXCHANGE RI_METRIC| Potential: Truncated Coulomb", &
1168 1 : "EXACT_EXCHANGE RI_METRIC| Range: ", xas_tdp_control%ri_m_potential%cutoff_radius &
1169 1 : *angstrom, ", (Ang)", &
1170 2 : "EXACT_EXCHANGE RI_METRIC| T_C_G_DATA: ", TRIM(xas_tdp_control%ri_m_potential%filename)
1171 1 : ELSE IF (xas_tdp_control%ri_m_potential%potential_type == do_potential_short) THEN
1172 : WRITE (UNIT=ou, FMT="(T3,A,/,T3,A,F5.2,A,/,T3,A,F5.2,A,/,T3,A,ES7.1)") &
1173 1 : "EXACT_EXCHANGE RI_METRIC| Potential: Short Range", &
1174 1 : "EXACT_EXCHANGE RI_METRIC| Omega: ", xas_tdp_control%ri_m_potential%omega, ", (1/a0)", &
1175 1 : "EXACT_EXCHANGE RI_METRIC| Effective Range: ", &
1176 1 : xas_tdp_control%ri_m_potential%cutoff_radius*angstrom, ", (Ang)", &
1177 2 : "EXACT_EXCHANGE RI_METRIC| EPS_RANGE: ", xas_tdp_control%eps_range
1178 : END IF
1179 : END IF
1180 : ELSE
1181 : WRITE (UNIT=ou, FMT="(/,T3,A,/)") &
1182 5 : "XAS_TDP| Exact Exchange Kernel: No "
1183 : END IF
1184 :
1185 : !overlap mtrix occupation
1186 : WRITE (UNIT=ou, FMT="(/,T3,A,F5.2)") &
1187 24 : "XAS_TDP| Overlap matrix occupation: ", occ
1188 :
1189 : !GW2X parameter
1190 24 : IF (xas_tdp_control%do_gw2x) THEN
1191 : WRITE (UNIT=ou, FMT="(T3,A,/)") &
1192 9 : "XAS_TDP| GW2X correction enabled"
1193 :
1194 9 : IF (xas_tdp_control%xps_only) THEN
1195 : WRITE (UNIT=ou, FMT="(T3,A)") &
1196 2 : "GW2X| Only computing ionizations potentials for XPS"
1197 : END IF
1198 :
1199 9 : IF (xas_tdp_control%pseudo_canonical) THEN
1200 : WRITE (UNIT=ou, FMT="(T3,A)") &
1201 8 : "GW2X| Using the pseudo-canonical scheme"
1202 : ELSE
1203 : WRITE (UNIT=ou, FMT="(T3,A)") &
1204 1 : "GW2X| Using the GW2X* scheme"
1205 : END IF
1206 :
1207 : WRITE (UNIT=ou, FMT="(T3,A,ES7.1)") &
1208 9 : "GW2X| EPS_GW2X: ", xas_tdp_control%gw2x_eps
1209 :
1210 : WRITE (UNIT=ou, FMT="(T3,A,I5)") &
1211 9 : "GW2X| contraction batch size: ", xas_tdp_control%batch_size
1212 :
1213 9 : IF ((INT(xas_tdp_control%c_os) .NE. 1) .OR. (INT(xas_tdp_control%c_ss) .NE. 1)) THEN
1214 : WRITE (UNIT=ou, FMT="(T3,A,F7.4,/,T3,A,F7.4)") &
1215 1 : "GW2X| Same-spin scaling factor: ", xas_tdp_control%c_ss, &
1216 2 : "GW2X| Opposite-spin scaling factor: ", xas_tdp_control%c_os
1217 : END IF
1218 :
1219 : END IF
1220 :
1221 48 : END SUBROUTINE print_info
1222 :
1223 : ! **************************************************************************************************
1224 : !> \brief Assosciate (possibly localized) lowest energy MOs to each excited atoms. The procedure
1225 : !> looks for MOs "centered" on the excited atoms by comparing distances. It
1226 : !> then fills the mos_of_ex_atoms arrays of the xas_tdp_env. Only the xas_tdp_control%n_search
1227 : !> lowest energy MOs are considered. Largely inspired by MI's implementation of XAS
1228 : !> It is assumed that the Berry phase is used to compute centers.
1229 : !> \param xas_tdp_env ...
1230 : !> \param xas_tdp_control ...
1231 : !> \param qs_env ...
1232 : !> \note Whether localization took place or not, the procedure is the same as centers are stored in
1233 : !> xas_tdp_env%qs_loc_env%localized_wfn_control%centers_set
1234 : !> Assumes that find_mo_centers has been run previously
1235 : ! **************************************************************************************************
1236 48 : SUBROUTINE assign_mos_to_ex_atoms(xas_tdp_env, xas_tdp_control, qs_env)
1237 :
1238 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1239 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1240 : TYPE(qs_environment_type), POINTER :: qs_env
1241 :
1242 : INTEGER :: at_index, iat, iat_memo, imo, ispin, &
1243 : n_atoms, n_search, nex_atoms, nspins
1244 : INTEGER, DIMENSION(3) :: perd_init
1245 48 : INTEGER, DIMENSION(:, :, :), POINTER :: mos_of_ex_atoms
1246 : REAL(dp) :: dist, dist_min
1247 : REAL(dp), DIMENSION(3) :: at_pos, r_ac, wfn_center
1248 : TYPE(cell_type), POINTER :: cell
1249 : TYPE(localized_wfn_control_type), POINTER :: localized_wfn_control
1250 48 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
1251 :
1252 48 : NULLIFY (localized_wfn_control, mos_of_ex_atoms, cell, particle_set)
1253 :
1254 : ! Initialization. mos_of_ex_atoms filled with -1, meaning no assigned state
1255 48 : mos_of_ex_atoms => xas_tdp_env%mos_of_ex_atoms
1256 524 : mos_of_ex_atoms(:, :, :) = -1
1257 48 : n_search = xas_tdp_control%n_search
1258 48 : nex_atoms = xas_tdp_env%nex_atoms
1259 48 : localized_wfn_control => xas_tdp_env%qs_loc_env%localized_wfn_control
1260 48 : CALL get_qs_env(qs_env=qs_env, particle_set=particle_set, cell=cell)
1261 48 : n_atoms = SIZE(particle_set)
1262 48 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
1263 :
1264 : ! Temporarly impose periodic BCs because of Berry's phase operator used for localization
1265 192 : perd_init = cell%perd
1266 192 : cell%perd = 1
1267 :
1268 : ! Loop over n_search lowest energy MOs and all atoms, for each spin
1269 102 : DO ispin = 1, nspins
1270 374 : DO imo = 1, n_search
1271 : ! retrieve MO wave function center coordinates.
1272 1088 : wfn_center(1:3) = localized_wfn_control%centers_set(ispin)%array(1:3, imo)
1273 272 : iat_memo = 0
1274 :
1275 : ! a large enough value to avoid bad surprises
1276 272 : dist_min = 10000.0_dp
1277 7590 : DO iat = 1, n_atoms
1278 29272 : at_pos = particle_set(iat)%r
1279 7318 : r_ac = pbc(at_pos, wfn_center, cell)
1280 29272 : dist = NORM2(r_ac)
1281 :
1282 : ! keep memory of which atom is the closest to the wave function center
1283 7590 : IF (dist < dist_min) THEN
1284 646 : iat_memo = iat
1285 646 : dist_min = dist
1286 : END IF
1287 : END DO
1288 :
1289 : ! Verify that the closest atom is actually excited and assign the MO if so
1290 556 : IF (ANY(xas_tdp_env%ex_atom_indices == iat_memo)) THEN
1291 114 : at_index = locate(xas_tdp_env%ex_atom_indices, iat_memo)
1292 114 : mos_of_ex_atoms(imo, at_index, ispin) = 1
1293 : END IF
1294 : END DO !imo
1295 : END DO !ispin
1296 :
1297 : ! Go back to initial BCs
1298 192 : cell%perd = perd_init
1299 :
1300 48 : END SUBROUTINE assign_mos_to_ex_atoms
1301 :
1302 : ! **************************************************************************************************
1303 : !> \brief Re-initialize the qs_loc_env to the current MOs.
1304 : !> \param qs_loc_env the env to re-initialize
1305 : !> \param n_loc_states the number of states to include
1306 : !> \param do_uks in cas of spin unrestricted calculation, initialize for both spins
1307 : !> \param qs_env ...
1308 : !> \note Useful when one needs to make use of qs_loc features and it is either with canonical MOs
1309 : !> or the localized MOs have been modified. do_localize is overwritten.
1310 : !> Same loc range for both spins
1311 : ! **************************************************************************************************
1312 80 : SUBROUTINE reinit_qs_loc_env(qs_loc_env, n_loc_states, do_uks, qs_env)
1313 :
1314 : TYPE(qs_loc_env_type), POINTER :: qs_loc_env
1315 : INTEGER, INTENT(IN) :: n_loc_states
1316 : LOGICAL, INTENT(IN) :: do_uks
1317 : TYPE(qs_environment_type), POINTER :: qs_env
1318 :
1319 : INTEGER :: i, nspins
1320 : TYPE(localized_wfn_control_type), POINTER :: loc_wfn_control
1321 :
1322 : ! First, release the old env
1323 80 : CALL qs_loc_env_release(qs_loc_env)
1324 :
1325 : ! Re-create it
1326 80 : CALL qs_loc_env_create(qs_loc_env)
1327 80 : CALL localized_wfn_control_create(qs_loc_env%localized_wfn_control)
1328 80 : loc_wfn_control => qs_loc_env%localized_wfn_control
1329 :
1330 : ! Initialize it
1331 80 : loc_wfn_control%localization_method = do_loc_none
1332 80 : loc_wfn_control%operator_type = op_loc_berry
1333 240 : loc_wfn_control%nloc_states(:) = n_loc_states
1334 80 : loc_wfn_control%eps_occ = 0.0_dp
1335 240 : loc_wfn_control%lu_bound_states(1, :) = 1
1336 240 : loc_wfn_control%lu_bound_states(2, :) = n_loc_states
1337 80 : loc_wfn_control%set_of_states = state_loc_list
1338 80 : loc_wfn_control%do_homo = .TRUE.
1339 240 : ALLOCATE (loc_wfn_control%loc_states(n_loc_states, 2))
1340 550 : DO i = 1, n_loc_states
1341 1490 : loc_wfn_control%loc_states(i, :) = i
1342 : END DO
1343 :
1344 80 : nspins = 1; IF (do_uks) nspins = 2
1345 80 : CALL set_loc_centers(loc_wfn_control, loc_wfn_control%nloc_states, nspins=nspins)
1346 : ! need to set do_localize=.TRUE. because otherwise no routine works
1347 80 : IF (do_uks) THEN
1348 8 : CALL qs_loc_env_init(qs_loc_env, loc_wfn_control, qs_env, do_localize=.TRUE.)
1349 : ELSE
1350 72 : CALL qs_loc_env_init(qs_loc_env, loc_wfn_control, qs_env, myspin=1, do_localize=.TRUE.)
1351 : END IF
1352 :
1353 80 : END SUBROUTINE reinit_qs_loc_env
1354 :
1355 : ! *************************************************************************************************
1356 : !> \brief Diagonalize the subset of previously localized MOs that are associated to each excited
1357 : !> atoms. Updates the MO coeffs accordingly.
1358 : !> \param xas_tdp_env ...
1359 : !> \param xas_tdp_control ...
1360 : !> \param qs_env ...
1361 : !> \note Needed because after localization, the MOs loose their identity (1s, 2s , 2p, etc)
1362 : ! **************************************************************************************************
1363 32 : SUBROUTINE diagonalize_assigned_mo_subset(xas_tdp_env, xas_tdp_control, qs_env)
1364 :
1365 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1366 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1367 : TYPE(qs_environment_type), POINTER :: qs_env
1368 :
1369 : INTEGER :: i, iat, ilmo, ispin, nao, nlmo, nspins
1370 32 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: evals
1371 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
1372 : TYPE(cp_fm_struct_type), POINTER :: ks_struct, lmo_struct
1373 : TYPE(cp_fm_type) :: evecs, ks_fm, lmo_fm, work
1374 : TYPE(cp_fm_type), POINTER :: mo_coeff
1375 32 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks
1376 32 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
1377 : TYPE(mp_para_env_type), POINTER :: para_env
1378 :
1379 32 : NULLIFY (mos, mo_coeff, matrix_ks, para_env, blacs_env, lmo_struct, ks_struct)
1380 :
1381 : ! Get what we need from qs_env
1382 32 : CALL get_qs_env(qs_env, mos=mos, matrix_ks=matrix_ks, para_env=para_env, blacs_env=blacs_env)
1383 :
1384 32 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
1385 :
1386 : ! Loop over the excited atoms and spin
1387 66 : DO ispin = 1, nspins
1388 110 : DO iat = 1, xas_tdp_env%nex_atoms
1389 :
1390 : ! get the MOs
1391 44 : CALL get_mo_set(mos(ispin), mo_coeff=mo_coeff, nao=nao)
1392 :
1393 : ! count how many MOs are associated to this atom and create a fm/struct
1394 342 : nlmo = COUNT(xas_tdp_env%mos_of_ex_atoms(:, iat, ispin) == 1)
1395 : CALL cp_fm_struct_create(lmo_struct, nrow_global=nao, ncol_global=nlmo, &
1396 44 : para_env=para_env, context=blacs_env)
1397 44 : CALL cp_fm_create(lmo_fm, lmo_struct)
1398 44 : CALL cp_fm_create(work, lmo_struct)
1399 :
1400 : CALL cp_fm_struct_create(ks_struct, nrow_global=nlmo, ncol_global=nlmo, &
1401 44 : para_env=para_env, context=blacs_env)
1402 44 : CALL cp_fm_create(ks_fm, ks_struct)
1403 44 : CALL cp_fm_create(evecs, ks_struct)
1404 :
1405 : ! Loop over the localized MOs associated to this atom
1406 44 : i = 0
1407 342 : DO ilmo = 1, xas_tdp_control%n_search
1408 298 : IF (xas_tdp_env%mos_of_ex_atoms(ilmo, iat, ispin) == -1) CYCLE
1409 :
1410 60 : i = i + 1
1411 : ! put the coeff in our atom-restricted lmo_fm
1412 : CALL cp_fm_to_fm_submat(mo_coeff, lmo_fm, nrow=nao, ncol=1, s_firstrow=1, &
1413 342 : s_firstcol=ilmo, t_firstrow=1, t_firstcol=i)
1414 :
1415 : END DO !ilmo
1416 :
1417 : ! Computing the KS matrix in the subset of MOs
1418 44 : CALL cp_dbcsr_sm_fm_multiply(matrix_ks(ispin)%matrix, lmo_fm, work, ncol=nlmo)
1419 44 : CALL parallel_gemm('T', 'N', nlmo, nlmo, nao, 1.0_dp, lmo_fm, work, 0.0_dp, ks_fm)
1420 :
1421 : ! Diagonalizing the KS matrix in the subset of MOs
1422 132 : ALLOCATE (evals(nlmo))
1423 44 : CALL cp_fm_syevd(ks_fm, evecs, evals)
1424 44 : DEALLOCATE (evals)
1425 :
1426 : ! Express the MOs in the basis that diagonalizes KS
1427 44 : CALL parallel_gemm('N', 'N', nao, nlmo, nlmo, 1.0_dp, lmo_fm, evecs, 0.0_dp, work)
1428 :
1429 : ! Replacing the new MOs back in the MO coeffs
1430 44 : i = 0
1431 342 : DO ilmo = 1, xas_tdp_control%n_search
1432 298 : IF (xas_tdp_env%mos_of_ex_atoms(ilmo, iat, ispin) == -1) CYCLE
1433 :
1434 60 : i = i + 1
1435 : CALL cp_fm_to_fm_submat(work, mo_coeff, nrow=nao, ncol=1, s_firstrow=1, &
1436 342 : s_firstcol=i, t_firstrow=1, t_firstcol=ilmo)
1437 :
1438 : END DO
1439 :
1440 : ! Excited atom clean-up
1441 44 : CALL cp_fm_release(lmo_fm)
1442 44 : CALL cp_fm_release(work)
1443 44 : CALL cp_fm_struct_release(lmo_struct)
1444 44 : CALL cp_fm_release(ks_fm)
1445 44 : CALL cp_fm_release(evecs)
1446 122 : CALL cp_fm_struct_release(ks_struct)
1447 : END DO !iat
1448 : END DO !ispin
1449 :
1450 64 : END SUBROUTINE diagonalize_assigned_mo_subset
1451 :
1452 : ! **************************************************************************************************
1453 : !> \brief Assign core MO(s) to a given donor_state, taking the type (1S, 2S, etc) into account.
1454 : !> The projection on a representative Slater-type orbital basis is used as a indicator.
1455 : !> It is assumed that MOs are already assigned to excited atoms based on their center
1456 : !> \param donor_state the donor_state to which a MO must be assigned
1457 : !> \param xas_tdp_env ...
1458 : !> \param xas_tdp_control ...
1459 : !> \param qs_env ...
1460 : ! **************************************************************************************************
1461 68 : SUBROUTINE assign_mos_to_donor_state(donor_state, xas_tdp_env, xas_tdp_control, qs_env)
1462 :
1463 : TYPE(donor_state_type), POINTER :: donor_state
1464 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1465 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1466 : TYPE(qs_environment_type), POINTER :: qs_env
1467 :
1468 : INTEGER :: at_index, i, iat, imo, ispin, l, my_mo, &
1469 : n_search, n_states, nao, ndo_so, nj, &
1470 : nsgf_kind, nsgf_sto, nspins, &
1471 : output_unit, zval
1472 68 : INTEGER, ALLOCATABLE, DIMENSION(:, :) :: my_mos
1473 : INTEGER, DIMENSION(2) :: next_best_overlap_ind
1474 : INTEGER, DIMENSION(4, 7) :: ne
1475 68 : INTEGER, DIMENSION(:), POINTER :: first_sgf, lq, nq
1476 68 : INTEGER, DIMENSION(:, :, :), POINTER :: mos_of_ex_atoms
1477 : LOGICAL :: unique
1478 : REAL(dp) :: zeff
1479 68 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: diag, overlap, sto_overlap
1480 68 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: max_overlap
1481 : REAL(dp), DIMENSION(2) :: next_best_overlap
1482 68 : REAL(dp), DIMENSION(:), POINTER :: mo_evals, zeta
1483 68 : REAL(dp), DIMENSION(:, :), POINTER :: overlap_matrix, tmp_coeff
1484 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
1485 : TYPE(cp_fm_struct_type), POINTER :: eval_mat_struct, gs_struct
1486 : TYPE(cp_fm_type) :: eval_mat, work_mat
1487 : TYPE(cp_fm_type), POINTER :: gs_coeffs, mo_coeff
1488 68 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks
1489 : TYPE(gto_basis_set_type), POINTER :: kind_basis_set, sto_to_gto_basis_set
1490 68 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
1491 : TYPE(mp_para_env_type), POINTER :: para_env
1492 68 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
1493 68 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
1494 : TYPE(sto_basis_set_type), POINTER :: sto_basis_set
1495 :
1496 68 : NULLIFY (sto_basis_set, sto_to_gto_basis_set, qs_kind_set, kind_basis_set, lq, nq, zeta)
1497 68 : NULLIFY (overlap_matrix, mos, mo_coeff, mos_of_ex_atoms, tmp_coeff, first_sgf, particle_set)
1498 68 : NULLIFY (mo_evals, matrix_ks, para_env, blacs_env)
1499 68 : NULLIFY (eval_mat_struct, gs_struct, gs_coeffs)
1500 :
1501 136 : output_unit = cp_logger_get_default_io_unit()
1502 :
1503 : CALL get_qs_env(qs_env=qs_env, qs_kind_set=qs_kind_set, mos=mos, particle_set=particle_set, &
1504 68 : matrix_ks=matrix_ks, para_env=para_env, blacs_env=blacs_env)
1505 :
1506 68 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
1507 :
1508 : ! Construction of a STO that fits the type of orbital we look for
1509 68 : ALLOCATE (zeta(1))
1510 68 : ALLOCATE (lq(1))
1511 68 : ALLOCATE (nq(1))
1512 : ! Retrieving quantum numbers
1513 68 : IF (donor_state%state_type == xas_1s_type) THEN
1514 54 : nq(1) = 1
1515 54 : lq(1) = 0
1516 54 : n_states = 1
1517 14 : ELSE IF (donor_state%state_type == xas_2s_type) THEN
1518 6 : nq(1) = 2
1519 6 : lq(1) = 0
1520 6 : n_states = 1
1521 8 : ELSE IF (donor_state%state_type == xas_2p_type) THEN
1522 8 : nq(1) = 2
1523 8 : lq(1) = 1
1524 8 : n_states = 3
1525 : ELSE
1526 0 : CPABORT("Procedure for required type not implemented")
1527 : END IF
1528 272 : ALLOCATE (my_mos(n_states, nspins))
1529 272 : ALLOCATE (max_overlap(n_states, nspins))
1530 :
1531 : ! Getting the atomic number
1532 68 : CALL get_qs_kind(qs_kind_set(donor_state%kind_index), zeff=zeff)
1533 68 : zval = INT(zeff)
1534 :
1535 : ! Electronic configuration (copied from MI's XAS)
1536 68 : ne = 0
1537 340 : DO l = 1, 4
1538 272 : nj = 2*(l - 1) + 1
1539 1836 : DO i = l, 7
1540 1496 : ne(l, i) = ptable(zval)%e_conv(l - 1) - 2*nj*(i - l)
1541 1496 : ne(l, i) = MAX(ne(l, i), 0)
1542 1768 : ne(l, i) = MIN(ne(l, i), 2*nj)
1543 : END DO
1544 : END DO
1545 :
1546 : ! computing zeta with the Slater sum rules
1547 68 : zeta(1) = srules(zval, ne, nq(1), lq(1))
1548 :
1549 : ! Allocating memory and initiate STO
1550 68 : CALL allocate_sto_basis_set(sto_basis_set)
1551 68 : CALL set_sto_basis_set(sto_basis_set, nshell=1, nq=nq, lq=lq, zet=zeta)
1552 :
1553 : ! Some clean-up
1554 68 : DEALLOCATE (nq, lq, zeta)
1555 :
1556 : ! Expanding the STO into (normalized) GTOs for later calculations, use standard 3 gaussians
1557 : CALL create_gto_from_sto_basis(sto_basis_set=sto_basis_set, &
1558 : gto_basis_set=sto_to_gto_basis_set, &
1559 68 : ngauss=3)
1560 68 : sto_to_gto_basis_set%norm_type = 2
1561 68 : CALL init_orb_basis_set(sto_to_gto_basis_set)
1562 :
1563 : ! Retrieving the atomic kind related GTO in which MOs are expanded
1564 68 : CALL get_qs_kind(qs_kind_set(donor_state%kind_index), basis_set=kind_basis_set)
1565 :
1566 : ! Allocating and computing the overlap between the two basis (they share the same center)
1567 68 : CALL get_gto_basis_set(gto_basis_set=kind_basis_set, nsgf=nsgf_kind)
1568 68 : CALL get_gto_basis_set(gto_basis_set=sto_to_gto_basis_set, nsgf=nsgf_sto)
1569 272 : ALLOCATE (overlap_matrix(nsgf_sto, nsgf_kind))
1570 :
1571 : ! Making use of MI's subroutine
1572 68 : CALL calc_stogto_overlap(sto_to_gto_basis_set, kind_basis_set, overlap_matrix)
1573 :
1574 : ! Some clean-up
1575 68 : CALL deallocate_sto_basis_set(sto_basis_set)
1576 68 : CALL deallocate_gto_basis_set(sto_to_gto_basis_set)
1577 :
1578 : ! Looping over the potential donor states to compute overlap with STO basis
1579 68 : mos_of_ex_atoms => xas_tdp_env%mos_of_ex_atoms
1580 68 : n_search = xas_tdp_control%n_search
1581 68 : at_index = donor_state%at_index
1582 68 : iat = locate(xas_tdp_env%ex_atom_indices, at_index)
1583 204 : ALLOCATE (first_sgf(SIZE(particle_set))) !probably do not need that
1584 68 : CALL get_particle_set(particle_set=particle_set, qs_kind_set=qs_kind_set, first_sgf=first_sgf)
1585 204 : ALLOCATE (tmp_coeff(nsgf_kind, 1))
1586 204 : ALLOCATE (sto_overlap(nsgf_kind))
1587 204 : ALLOCATE (overlap(n_search))
1588 :
1589 68 : next_best_overlap = 0.0_dp
1590 240 : max_overlap = 0.0_dp
1591 :
1592 144 : DO ispin = 1, nspins
1593 :
1594 76 : CALL get_mo_set(mos(ispin), mo_coeff=mo_coeff, nao=nao)
1595 482 : overlap = 0.0_dp
1596 :
1597 76 : my_mo = 0
1598 482 : DO imo = 1, n_search
1599 482 : IF (mos_of_ex_atoms(imo, iat, ispin) > 0) THEN
1600 :
1601 3960 : sto_overlap = 0.0_dp
1602 4124 : tmp_coeff = 0.0_dp
1603 :
1604 : ! Getting the relevant coefficients for the candidate state
1605 : CALL cp_fm_get_submatrix(fm=mo_coeff, target_m=tmp_coeff, start_row=first_sgf(at_index), &
1606 164 : start_col=imo, n_rows=nsgf_kind, n_cols=1, transpose=.FALSE.)
1607 :
1608 : ! Computing the product overlap_matrix*coeffs
1609 : CALL dgemm('N', 'N', nsgf_sto, 1, nsgf_kind, 1.0_dp, overlap_matrix, nsgf_sto, &
1610 164 : tmp_coeff, nsgf_kind, 0.0_dp, sto_overlap, nsgf_sto)
1611 :
1612 : ! Each element of column vector sto_overlap is the overlap of a basis element of the
1613 : ! generated STO basis with the kind specific orbital basis. Take the sum of the absolute
1614 : ! values so that rotation (of the px, py, pz for example) does not hinder our search
1615 3960 : overlap(imo) = SUM(ABS(sto_overlap))
1616 :
1617 : END IF
1618 : END DO
1619 :
1620 : ! Finding the best overlap(s)
1621 172 : DO i = 1, n_states
1622 602 : my_mo = MAXLOC(overlap, 1)
1623 96 : my_mos(i, ispin) = my_mo
1624 698 : max_overlap(i, ispin) = MAXVAL(overlap, 1)
1625 172 : overlap(my_mo) = 0.0_dp
1626 : END DO
1627 : ! Getting the next best overlap (for validation purposes)
1628 558 : next_best_overlap(ispin) = MAXVAL(overlap, 1)
1629 482 : next_best_overlap_ind(ispin) = MAXLOC(overlap, 1)
1630 :
1631 : ! Sort MO indices
1632 220 : CALL sort_unique(my_mos(:, ispin), unique)
1633 :
1634 : END DO !ispin
1635 :
1636 : ! Some clean-up
1637 68 : DEALLOCATE (overlap_matrix, tmp_coeff)
1638 :
1639 : ! Dealing with the result
1640 480 : IF (ALL(my_mos > 0) .AND. ALL(my_mos <= n_search)) THEN
1641 : ! Assigning the MO indices to the donor_state
1642 272 : ALLOCATE (donor_state%mo_indices(n_states, nspins))
1643 240 : donor_state%mo_indices = my_mos
1644 68 : donor_state%ndo_mo = n_states
1645 :
1646 : ! Storing the MOs in the donor_state, as vectors column: first columns alpha spin, then beta
1647 : CALL cp_fm_struct_create(gs_struct, nrow_global=nao, ncol_global=n_states*nspins, &
1648 68 : para_env=para_env, context=blacs_env)
1649 68 : ALLOCATE (donor_state%gs_coeffs)
1650 68 : CALL cp_fm_create(donor_state%gs_coeffs, gs_struct)
1651 :
1652 144 : DO ispin = 1, nspins
1653 76 : CALL get_mo_set(mos(ispin), mo_coeff=mo_coeff)
1654 240 : DO i = 1, n_states
1655 : CALL cp_fm_to_fm_submat(msource=mo_coeff, mtarget=donor_state%gs_coeffs, nrow=nao, &
1656 : ncol=1, s_firstrow=1, s_firstcol=my_mos(i, ispin), &
1657 172 : t_firstrow=1, t_firstcol=(ispin - 1)*n_states + i)
1658 : END DO
1659 : END DO
1660 68 : gs_coeffs => donor_state%gs_coeffs
1661 :
1662 : !Keep the subset of the coeffs centered on the excited atom as global array (used a lot)
1663 272 : ALLOCATE (donor_state%contract_coeffs(nsgf_kind, n_states*nspins))
1664 : CALL cp_fm_get_submatrix(gs_coeffs, donor_state%contract_coeffs, start_row=first_sgf(at_index), &
1665 68 : start_col=1, n_rows=nsgf_kind, n_cols=n_states*nspins)
1666 :
1667 : ! Assigning corresponding energy eigenvalues and writing some info in standard input file
1668 :
1669 : !standard eigenvalues as gotten from the KS diagonalization in the ground state
1670 68 : IF (.NOT. xas_tdp_control%do_loc .AND. .NOT. xas_tdp_control%do_roks) THEN
1671 20 : IF (output_unit > 0) THEN
1672 : WRITE (UNIT=output_unit, FMT="(T5,A,/,T5,A,/,T5,A)") &
1673 10 : "The following canonical MO(s) have been associated with the donor state(s)", &
1674 10 : "based on the overlap with the components of a minimal STO basis: ", &
1675 20 : " Spin MO index overlap(sum)"
1676 : END IF
1677 :
1678 80 : ALLOCATE (donor_state%energy_evals(n_states, nspins))
1679 80 : donor_state%energy_evals = 0.0_dp
1680 :
1681 : ! Canonical MO, no change in eigenvalues, only diagonal elements
1682 44 : DO ispin = 1, nspins
1683 24 : CALL get_mo_set(mos(ispin), eigenvalues=mo_evals)
1684 80 : DO i = 1, n_states
1685 36 : donor_state%energy_evals(i, ispin) = mo_evals(my_mos(i, ispin))
1686 :
1687 60 : IF (output_unit > 0) THEN
1688 : WRITE (UNIT=output_unit, FMT="(T46,I4,I11,F17.5)") &
1689 18 : ispin, my_mos(i, ispin), max_overlap(i, ispin)
1690 : END IF
1691 : END DO
1692 : END DO
1693 :
1694 : !either localization of MOs or ROKS, in both cases the MO eigenvalues from the KS
1695 : !digonalization mat have changed
1696 : ELSE
1697 48 : IF (output_unit > 0) THEN
1698 : WRITE (UNIT=output_unit, FMT="(T5,A,/,T5,A,/,T5,A)") &
1699 24 : "The following localized MO(s) have been associated with the donor state(s)", &
1700 24 : "based on the overlap with the components of a minimal STO basis: ", &
1701 48 : " Spin MO index overlap(sum)"
1702 : END IF
1703 :
1704 : ! Loop over the donor states and print
1705 100 : DO ispin = 1, nspins
1706 160 : DO i = 1, n_states
1707 :
1708 : ! Print info
1709 112 : IF (output_unit > 0) THEN
1710 : WRITE (UNIT=output_unit, FMT="(T46,I4,I11,F17.5)") &
1711 30 : ispin, my_mos(i, ispin), max_overlap(i, ispin)
1712 : END IF
1713 : END DO
1714 : END DO
1715 :
1716 : ! MO have been rotated or non-physical ROKS MO eigrenvalues:
1717 : ! => need epsilon_ij = <psi_i|F|psi_j> = sum_{pq} c_{qi}c_{pj} F_{pq}
1718 : ! Note: only have digonal elements by construction
1719 48 : ndo_so = nspins*n_states
1720 48 : CALL cp_fm_create(work_mat, gs_struct)
1721 : CALL cp_fm_struct_create(eval_mat_struct, nrow_global=ndo_so, ncol_global=ndo_so, &
1722 48 : para_env=para_env, context=blacs_env)
1723 48 : CALL cp_fm_create(eval_mat, eval_mat_struct)
1724 144 : ALLOCATE (diag(ndo_so))
1725 :
1726 48 : IF (.NOT. xas_tdp_control%do_roks) THEN
1727 :
1728 192 : ALLOCATE (donor_state%energy_evals(n_states, nspins))
1729 160 : donor_state%energy_evals = 0.0_dp
1730 :
1731 : ! Compute gs_coeff^T * matrix_ks * gs_coeff to get the epsilon_ij matrix
1732 100 : DO ispin = 1, nspins
1733 52 : CALL cp_dbcsr_sm_fm_multiply(matrix_ks(ispin)%matrix, gs_coeffs, work_mat, ncol=ndo_so)
1734 52 : CALL parallel_gemm('T', 'N', ndo_so, ndo_so, nao, 1.0_dp, gs_coeffs, work_mat, 0.0_dp, eval_mat)
1735 :
1736 : ! Put the epsilon_ii into the donor_state. No off-diagonal element because of subset diag
1737 52 : CALL cp_fm_get_diag(eval_mat, diag)
1738 160 : donor_state%energy_evals(:, ispin) = diag((ispin - 1)*n_states + 1:ispin*n_states)
1739 :
1740 : END DO
1741 :
1742 : ELSE
1743 : ! If ROKS, slightly different procedure => 2 KS matrices but one type of MOs
1744 0 : ALLOCATE (donor_state%energy_evals(n_states, 2))
1745 0 : donor_state%energy_evals = 0.0_dp
1746 :
1747 : ! Compute gs_coeff^T * matrix_ks * gs_coeff to get the epsilon_ij matrix
1748 0 : DO ispin = 1, 2
1749 0 : CALL cp_dbcsr_sm_fm_multiply(matrix_ks(ispin)%matrix, gs_coeffs, work_mat, ncol=ndo_so)
1750 0 : CALL parallel_gemm('T', 'N', ndo_so, ndo_so, nao, 1.0_dp, gs_coeffs, work_mat, 0.0_dp, eval_mat)
1751 :
1752 0 : CALL cp_fm_get_diag(eval_mat, diag)
1753 0 : donor_state%energy_evals(:, ispin) = diag(:)
1754 :
1755 : END DO
1756 :
1757 0 : DEALLOCATE (diag)
1758 : END IF
1759 :
1760 : ! Clean-up
1761 48 : CALL cp_fm_release(work_mat)
1762 48 : CALL cp_fm_release(eval_mat)
1763 48 : CALL cp_fm_struct_release(eval_mat_struct)
1764 :
1765 : END IF ! do_localize and/or ROKS
1766 :
1767 : ! Allocate and initialize GW2X corrected IPs as energy_evals
1768 272 : ALLOCATE (donor_state%gw2x_evals(SIZE(donor_state%energy_evals, 1), SIZE(donor_state%energy_evals, 2)))
1769 240 : donor_state%gw2x_evals(:, :) = donor_state%energy_evals(:, :)
1770 :
1771 : ! Clean-up
1772 68 : CALL cp_fm_struct_release(gs_struct)
1773 68 : DEALLOCATE (first_sgf)
1774 :
1775 68 : IF (output_unit > 0) WRITE (UNIT=output_unit, FMT="(T5,A)") " "
1776 :
1777 144 : DO ispin = 1, nspins
1778 144 : IF (output_unit > 0) THEN
1779 : WRITE (UNIT=output_unit, FMT="(T5,A,I1,A,F7.5,A,I4)") &
1780 38 : "The next best overlap for spin ", ispin, " is ", next_best_overlap(ispin), &
1781 76 : " for MO with index ", next_best_overlap_ind(ispin)
1782 : END IF
1783 : END DO
1784 68 : IF (output_unit > 0) WRITE (UNIT=output_unit, FMT="(T5,A)") " "
1785 :
1786 : ELSE
1787 0 : CPABORT("A core donor state could not be assigned MO(s). Increasing NSEARCH might help.")
1788 : END IF
1789 :
1790 272 : END SUBROUTINE assign_mos_to_donor_state
1791 :
1792 : ! **************************************************************************************************
1793 : !> \brief Compute the centers and spreads of (core) MOs using the Berry phase operator
1794 : !> \param xas_tdp_env ...
1795 : !> \param xas_tdp_control ...
1796 : !> \param qs_env ...
1797 : !> \note xas_tdp_env%qs_loc_env is used and modified. OK since no localization done after this
1798 : !> subroutine is used.
1799 : ! **************************************************************************************************
1800 80 : SUBROUTINE find_mo_centers(xas_tdp_env, xas_tdp_control, qs_env)
1801 :
1802 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1803 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1804 : TYPE(qs_environment_type), POINTER :: qs_env
1805 :
1806 : INTEGER :: dim_op, i, ispin, j, n_centers, nao, &
1807 : nspins
1808 : REAL(dp), DIMENSION(6) :: weights
1809 : TYPE(cell_type), POINTER :: cell
1810 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
1811 : TYPE(cp_fm_struct_type), POINTER :: tmp_fm_struct
1812 : TYPE(cp_fm_type) :: opvec
1813 80 : TYPE(cp_fm_type), ALLOCATABLE, DIMENSION(:, :) :: zij_fm_set
1814 80 : TYPE(cp_fm_type), DIMENSION(:), POINTER :: moloc_coeff
1815 : TYPE(cp_fm_type), POINTER :: vectors
1816 80 : TYPE(dbcsr_p_type), DIMENSION(:, :), POINTER :: op_sm_set
1817 : TYPE(mp_para_env_type), POINTER :: para_env
1818 : TYPE(qs_loc_env_type), POINTER :: qs_loc_env
1819 : TYPE(section_vals_type), POINTER :: print_loc_section, prog_run_info
1820 :
1821 80 : NULLIFY (qs_loc_env, cell, print_loc_section, op_sm_set, moloc_coeff, vectors)
1822 80 : NULLIFY (tmp_fm_struct, para_env, blacs_env, prog_run_info)
1823 :
1824 : ! Initialization
1825 80 : print_loc_section => xas_tdp_control%print_loc_subsection
1826 80 : n_centers = xas_tdp_control%n_search
1827 80 : CALL get_qs_env(qs_env=qs_env, para_env=para_env, blacs_env=blacs_env, cell=cell)
1828 :
1829 : ! Set print option to debug to keep clean output file
1830 80 : prog_run_info => section_vals_get_subs_vals(print_loc_section, "PROGRAM_RUN_INFO")
1831 : CALL section_vals_val_set(prog_run_info, keyword_name="_SECTION_PARAMETERS_", &
1832 80 : i_val=debug_print_level)
1833 :
1834 : ! Re-initialize the qs_loc_env to get the current MOs. Use force_loc because needed for centers
1835 80 : CALL reinit_qs_loc_env(xas_tdp_env%qs_loc_env, n_centers, xas_tdp_control%do_uks, qs_env)
1836 80 : qs_loc_env => xas_tdp_env%qs_loc_env
1837 :
1838 : ! Get what we need from the qs_lovc_env
1839 : CALL get_qs_loc_env(qs_loc_env=qs_loc_env, weights=weights, op_sm_set=op_sm_set, &
1840 80 : moloc_coeff=moloc_coeff)
1841 :
1842 : ! Prepare for zij
1843 80 : vectors => moloc_coeff(1)
1844 80 : CALL cp_fm_get_info(vectors, nrow_global=nao)
1845 80 : CALL cp_fm_create(opvec, vectors%matrix_struct)
1846 :
1847 : CALL cp_fm_struct_create(tmp_fm_struct, para_env=para_env, context=blacs_env, &
1848 80 : ncol_global=n_centers, nrow_global=n_centers)
1849 :
1850 80 : IF (cell%orthorhombic) THEN
1851 : dim_op = 3
1852 : ELSE
1853 0 : dim_op = 6
1854 : END IF
1855 960 : ALLOCATE (zij_fm_set(2, dim_op))
1856 320 : DO i = 1, dim_op
1857 800 : DO j = 1, 2
1858 720 : CALL cp_fm_create(zij_fm_set(j, i), tmp_fm_struct)
1859 : END DO
1860 : END DO
1861 :
1862 : ! If spin-unrestricted, need to go spin by spin
1863 80 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
1864 :
1865 168 : DO ispin = 1, nspins
1866 : ! zij computation, copied from qs_loc_methods:optimize_loc_berry
1867 88 : vectors => moloc_coeff(ispin)
1868 352 : DO i = 1, dim_op
1869 880 : DO j = 1, 2
1870 528 : CALL cp_fm_set_all(zij_fm_set(j, i), 0.0_dp)
1871 528 : CALL cp_dbcsr_sm_fm_multiply(op_sm_set(j, i)%matrix, vectors, opvec, ncol=n_centers)
1872 : CALL parallel_gemm("T", "N", n_centers, n_centers, nao, 1.0_dp, vectors, opvec, 0.0_dp, &
1873 792 : zij_fm_set(j, i))
1874 : END DO
1875 : END DO
1876 :
1877 : ! Compute centers (and spread)
1878 : CALL centers_spreads_berry(qs_loc_env=qs_loc_env, zij=zij_fm_set, nmoloc=n_centers, &
1879 : cell=cell, weights=weights, ispin=ispin, &
1880 168 : print_loc_section=print_loc_section, only_initial_out=.TRUE.)
1881 : END DO !ispins
1882 :
1883 : ! Clean-up
1884 80 : CALL cp_fm_release(opvec)
1885 80 : CALL cp_fm_struct_release(tmp_fm_struct)
1886 80 : CALL cp_fm_release(zij_fm_set)
1887 :
1888 : ! Make sure we leave with the correct do_loc value
1889 80 : qs_loc_env%do_localize = xas_tdp_control%do_loc
1890 :
1891 240 : END SUBROUTINE find_mo_centers
1892 :
1893 : ! **************************************************************************************************
1894 : !> \brief Prints the MO to donor_state assocaition with overlap and Mulliken population analysis
1895 : !> \param xas_tdp_env ...
1896 : !> \param xas_tdp_control ...
1897 : !> \param qs_env ...
1898 : !> \note Called only in case of CHECK_ONLY run
1899 : ! **************************************************************************************************
1900 0 : SUBROUTINE print_checks(xas_tdp_env, xas_tdp_control, qs_env)
1901 :
1902 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1903 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1904 : TYPE(qs_environment_type), POINTER :: qs_env
1905 :
1906 : CHARACTER(LEN=default_string_length) :: kind_name
1907 : INTEGER :: current_state_index, iat, iatom, ikind, &
1908 : istate, output_unit, tmp_index
1909 0 : INTEGER, DIMENSION(:), POINTER :: atoms_of_kind
1910 0 : TYPE(atomic_kind_type), DIMENSION(:), POINTER :: atomic_kind_set
1911 : TYPE(donor_state_type), POINTER :: current_state
1912 :
1913 0 : NULLIFY (atomic_kind_set, atoms_of_kind, current_state)
1914 :
1915 0 : output_unit = cp_logger_get_default_io_unit()
1916 :
1917 0 : IF (output_unit > 0) THEN
1918 : WRITE (output_unit, "(/,T3,A,/,T3,A,/,T3,A)") &
1919 0 : "# Check the donor states for their quality. They need to have a well defined type ", &
1920 0 : " (1s, 2s, etc) which is indicated by the overlap. They also need to be localized, ", &
1921 0 : " for which the Mulliken population analysis is one indicator (must be close to 1.0)"
1922 : END IF
1923 :
1924 : ! Loop over the donor states (as in the main xas_tdp loop)
1925 0 : CALL get_qs_env(qs_env=qs_env, atomic_kind_set=atomic_kind_set)
1926 0 : current_state_index = 1
1927 :
1928 : !loop over atomic kinds
1929 0 : DO ikind = 1, SIZE(atomic_kind_set)
1930 :
1931 : CALL get_atomic_kind(atomic_kind=atomic_kind_set(ikind), name=kind_name, &
1932 0 : atom_list=atoms_of_kind)
1933 :
1934 0 : IF (.NOT. ANY(xas_tdp_env%ex_kind_indices == ikind)) CYCLE
1935 :
1936 : !loop over atoms of kind
1937 0 : DO iat = 1, SIZE(atoms_of_kind)
1938 0 : iatom = atoms_of_kind(iat)
1939 :
1940 0 : IF (.NOT. ANY(xas_tdp_env%ex_atom_indices == iatom)) CYCLE
1941 0 : tmp_index = locate(xas_tdp_env%ex_atom_indices, iatom)
1942 :
1943 : !loop over states of excited atom
1944 0 : DO istate = 1, SIZE(xas_tdp_env%state_types, 1)
1945 :
1946 0 : IF (xas_tdp_env%state_types(istate, tmp_index) == xas_not_excited) CYCLE
1947 :
1948 0 : current_state => xas_tdp_env%donor_states(current_state_index)
1949 : CALL set_donor_state(current_state, at_index=iatom, &
1950 : at_symbol=kind_name, kind_index=ikind, &
1951 0 : state_type=xas_tdp_env%state_types(istate, tmp_index))
1952 :
1953 0 : IF (output_unit > 0) THEN
1954 : WRITE (output_unit, "(/,T4,A,A2,A,I4,A,A,A)") &
1955 0 : "-Donor state of type ", xas_tdp_env%state_type_char(current_state%state_type), &
1956 0 : " for atom", current_state%at_index, " of kind ", TRIM(current_state%at_symbol), ":"
1957 : END IF
1958 :
1959 : !Assign the MOs and perform Mulliken
1960 0 : CALL assign_mos_to_donor_state(current_state, xas_tdp_env, xas_tdp_control, qs_env)
1961 0 : CALL perform_mulliken_on_donor_state(current_state, qs_env)
1962 :
1963 0 : current_state_index = current_state_index + 1
1964 0 : NULLIFY (current_state)
1965 :
1966 : END DO !istate
1967 : END DO !iat
1968 : END DO !ikind
1969 :
1970 0 : IF (output_unit > 0) THEN
1971 : WRITE (output_unit, "(/,T5,A)") &
1972 0 : "Use LOCALIZE and/or increase N_SEARCH for better results, if so required."
1973 : END IF
1974 :
1975 0 : END SUBROUTINE print_checks
1976 :
1977 : ! **************************************************************************************************
1978 : !> \brief Computes the required multipole moment in the length representation for a given atom
1979 : !> \param iatom index of the given atom
1980 : !> \param xas_tdp_env ...
1981 : !> \param xas_tdp_control ...
1982 : !> \param qs_env ...
1983 : !> \note Assumes that wither dipole or quadrupole in length rep is required
1984 : ! **************************************************************************************************
1985 24 : SUBROUTINE compute_lenrep_multipole(iatom, xas_tdp_env, xas_tdp_control, qs_env)
1986 :
1987 : INTEGER, INTENT(IN) :: iatom
1988 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
1989 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
1990 : TYPE(qs_environment_type), POINTER :: qs_env
1991 :
1992 : INTEGER :: i, order
1993 : REAL(dp), DIMENSION(3) :: rc
1994 24 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: work
1995 24 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
1996 :
1997 24 : NULLIFY (work, particle_set)
1998 :
1999 24 : CALL get_qs_env(qs_env, particle_set=particle_set)
2000 96 : rc = particle_set(iatom)%r
2001 :
2002 240 : ALLOCATE (work(9))
2003 24 : IF (xas_tdp_control%dipole_form == xas_dip_len) THEN
2004 96 : DO i = 1, 3
2005 72 : CALL dbcsr_set(xas_tdp_env%dipmat(i)%matrix, 0.0_dp)
2006 96 : work(i)%matrix => xas_tdp_env%dipmat(i)%matrix
2007 : END DO
2008 24 : order = 1
2009 : END IF
2010 24 : IF (xas_tdp_control%do_quad) THEN
2011 0 : DO i = 1, 6
2012 0 : CALL dbcsr_set(xas_tdp_env%quadmat(i)%matrix, 0.0_dp)
2013 0 : work(3 + i)%matrix => xas_tdp_env%quadmat(i)%matrix
2014 : END DO
2015 0 : order = 2
2016 0 : IF (xas_tdp_control%dipole_form == xas_dip_vel) order = -2
2017 : END IF
2018 :
2019 : !enforce minimum image to avoid PBCs related issues, ok because localized densities
2020 24 : CALL rRc_xyz_ao(work, qs_env, rc, order=order, minimum_image=.TRUE.)
2021 24 : DEALLOCATE (work)
2022 :
2023 24 : END SUBROUTINE compute_lenrep_multipole
2024 :
2025 : ! **************************************************************************************************
2026 : !> \brief Computes the oscillator strength based on the dipole moment (velocity or length rep) for
2027 : !> all available excitation energies and store the results in the donor_state. There is no
2028 : !> triplet dipole in the spin-restricted ground state.
2029 : !> \param donor_state the donor state which is excited
2030 : !> \param xas_tdp_control ...
2031 : !> \param xas_tdp_env ...
2032 : !> \note The oscillator strength is a scalar: osc_str = 2/(3*omega)*(dipole_v)^2 in the velocity rep
2033 : !> or : osc_str = 2/3*omega*(dipole_r)^2 in the length representation
2034 : !> The formulae for the dipoles come from the trace of the dipole operator with the transition
2035 : !> densities, i.e. what we get from solving the xas_tdp problem. Same procedure with or wo TDA
2036 : ! **************************************************************************************************
2037 56 : SUBROUTINE compute_dipole_fosc(donor_state, xas_tdp_control, xas_tdp_env)
2038 :
2039 : TYPE(donor_state_type), POINTER :: donor_state
2040 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2041 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2042 :
2043 : CHARACTER(len=*), PARAMETER :: routineN = 'compute_dipole_fosc'
2044 :
2045 : INTEGER :: handle, iosc, j, nao, ndo_mo, ndo_so, &
2046 : ngs, nosc, nspins
2047 : LOGICAL :: do_sc, do_sg
2048 : REAL(dp) :: osc_xyz, pref
2049 56 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: tot_contr
2050 56 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: dip_block
2051 56 : REAL(dp), DIMENSION(:), POINTER :: lr_evals
2052 56 : REAL(dp), DIMENSION(:, :), POINTER :: osc_str
2053 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2054 : TYPE(cp_fm_struct_type), POINTER :: col_struct, mat_struct
2055 : TYPE(cp_fm_type) :: col_work, mat_work
2056 : TYPE(cp_fm_type), POINTER :: lr_coeffs
2057 56 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: dipmat
2058 : TYPE(mp_para_env_type), POINTER :: para_env
2059 :
2060 56 : NULLIFY (dipmat, col_struct, mat_struct, para_env, blacs_env, lr_coeffs)
2061 56 : NULLIFY (lr_evals, osc_str)
2062 :
2063 56 : CALL timeset(routineN, handle)
2064 :
2065 : ! Initialization
2066 56 : do_sc = xas_tdp_control%do_spin_cons
2067 56 : do_sg = xas_tdp_control%do_singlet
2068 56 : IF (do_sc) THEN
2069 8 : nspins = 2
2070 8 : lr_evals => donor_state%sc_evals
2071 8 : lr_coeffs => donor_state%sc_coeffs
2072 48 : ELSE IF (do_sg) THEN
2073 48 : nspins = 1
2074 48 : lr_evals => donor_state%sg_evals
2075 48 : lr_coeffs => donor_state%sg_coeffs
2076 : ELSE
2077 0 : CPABORT("Dipole oscilaltor strength only for singlets and spin-conserving excitations.")
2078 : END IF
2079 56 : ndo_mo = donor_state%ndo_mo
2080 56 : ndo_so = ndo_mo*nspins
2081 56 : ngs = ndo_so; IF (xas_tdp_control%do_roks) ngs = ndo_mo !in ROKS, same gs coeffs
2082 56 : nosc = SIZE(lr_evals)
2083 168 : ALLOCATE (donor_state%osc_str(nosc, 4))
2084 56 : osc_str => donor_state%osc_str
2085 3704 : osc_str = 0.0_dp
2086 56 : dipmat => xas_tdp_env%dipmat
2087 :
2088 : ! do some work matrix initialization
2089 : CALL cp_fm_get_info(donor_state%gs_coeffs, matrix_struct=col_struct, para_env=para_env, &
2090 56 : context=blacs_env, nrow_global=nao)
2091 : CALL cp_fm_struct_create(mat_struct, para_env=para_env, context=blacs_env, &
2092 56 : nrow_global=ndo_so*nosc, ncol_global=ngs)
2093 56 : CALL cp_fm_create(mat_work, mat_struct)
2094 56 : CALL cp_fm_create(col_work, col_struct)
2095 :
2096 336 : ALLOCATE (tot_contr(ndo_mo), dip_block(ndo_so, ngs))
2097 56 : pref = 2.0_dp; IF (do_sc) pref = 1.0_dp !because of singlet definition u = 1/sqrt(2)(c_a+c_b)
2098 :
2099 : ! Looping over cartesian coord
2100 224 : DO j = 1, 3
2101 :
2102 : !Compute dip*gs_coeffs
2103 168 : CALL cp_dbcsr_sm_fm_multiply(dipmat(j)%matrix, donor_state%gs_coeffs, col_work, ncol=ngs)
2104 : !compute lr_coeffs*dip*gs_coeffs
2105 168 : CALL parallel_gemm('T', 'N', ndo_so*nosc, ngs, nao, 1.0_dp, lr_coeffs, col_work, 0.0_dp, mat_work)
2106 :
2107 : !Loop over the excited states
2108 2792 : DO iosc = 1, nosc
2109 :
2110 5424 : tot_contr = 0.0_dp
2111 : CALL cp_fm_get_submatrix(fm=mat_work, target_m=dip_block, start_row=(iosc - 1)*ndo_so + 1, &
2112 2568 : start_col=1, n_rows=ndo_so, n_cols=ngs)
2113 2568 : IF (do_sg) THEN
2114 1944 : tot_contr(:) = get_diag(dip_block)
2115 624 : ELSE IF (do_sc .AND. xas_tdp_control%do_uks) THEN
2116 624 : tot_contr(:) = get_diag(dip_block(1:ndo_mo, 1:ndo_mo)) !alpha
2117 1392 : tot_contr(:) = tot_contr(:) + get_diag(dip_block(ndo_mo + 1:ndo_so, ndo_mo + 1:ndo_so)) !beta
2118 : ELSE
2119 : !roks
2120 0 : tot_contr(:) = get_diag(dip_block(1:ndo_mo, :)) !alpha
2121 0 : tot_contr(:) = tot_contr(:) + get_diag(dip_block(ndo_mo + 1:ndo_so, :)) !beta
2122 : END IF
2123 :
2124 5424 : osc_xyz = SUM(tot_contr)**2
2125 2568 : osc_str(iosc, 4) = osc_str(iosc, 4) + osc_xyz
2126 2736 : osc_str(iosc, j) = osc_xyz
2127 :
2128 : END DO !iosc
2129 : END DO !j
2130 :
2131 : !compute the prefactor
2132 280 : DO j = 1, 4
2133 280 : IF (xas_tdp_control%dipole_form == xas_dip_len) THEN
2134 3248 : osc_str(:, j) = pref*2.0_dp/3.0_dp*lr_evals(:)*osc_str(:, j)
2135 : ELSE
2136 4048 : osc_str(:, j) = pref*2.0_dp/3.0_dp/lr_evals(:)*osc_str(:, j)
2137 : END IF
2138 : END DO
2139 :
2140 : !clean-up
2141 56 : CALL cp_fm_release(mat_work)
2142 56 : CALL cp_fm_release(col_work)
2143 56 : CALL cp_fm_struct_release(mat_struct)
2144 :
2145 56 : CALL timestop(handle)
2146 :
2147 168 : END SUBROUTINE compute_dipole_fosc
2148 :
2149 : ! **************************************************************************************************
2150 : !> \brief Computes the oscillator strength due to the electric quadrupole moment and store it in
2151 : !> the donor_state (for singlet or spin-conserving)
2152 : !> \param donor_state the donor state which is excited
2153 : !> \param xas_tdp_control ...
2154 : !> \param xas_tdp_env ...
2155 : !> \note Formula: 1/20*a_fine^2*omega^3 * sum_ab (sum_i r_ia*r_ib - 1/3*ri^2*delta_ab)
2156 : ! **************************************************************************************************
2157 0 : SUBROUTINE compute_quadrupole_fosc(donor_state, xas_tdp_control, xas_tdp_env)
2158 :
2159 : TYPE(donor_state_type), POINTER :: donor_state
2160 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2161 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2162 :
2163 : CHARACTER(len=*), PARAMETER :: routineN = 'compute_quadrupole_fosc'
2164 :
2165 : INTEGER :: handle, iosc, j, nao, ndo_mo, ndo_so, &
2166 : ngs, nosc, nspins
2167 : LOGICAL :: do_sc, do_sg
2168 : REAL(dp) :: pref
2169 0 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: tot_contr, trace
2170 0 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: quad_block
2171 0 : REAL(dp), DIMENSION(:), POINTER :: lr_evals, osc_str
2172 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2173 : TYPE(cp_fm_struct_type), POINTER :: col_struct, mat_struct
2174 : TYPE(cp_fm_type) :: col_work, mat_work
2175 : TYPE(cp_fm_type), POINTER :: lr_coeffs
2176 0 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: quadmat
2177 : TYPE(mp_para_env_type), POINTER :: para_env
2178 :
2179 0 : NULLIFY (lr_evals, osc_str, lr_coeffs, col_struct, mat_struct, para_env)
2180 0 : NULLIFY (blacs_env)
2181 :
2182 0 : CALL timeset(routineN, handle)
2183 :
2184 : ! Initialization
2185 0 : do_sc = xas_tdp_control%do_spin_cons
2186 0 : do_sg = xas_tdp_control%do_singlet
2187 0 : IF (do_sc) THEN
2188 0 : nspins = 2
2189 0 : lr_evals => donor_state%sc_evals
2190 0 : lr_coeffs => donor_state%sc_coeffs
2191 0 : ELSE IF (do_sg) THEN
2192 0 : nspins = 1
2193 0 : lr_evals => donor_state%sg_evals
2194 0 : lr_coeffs => donor_state%sg_coeffs
2195 : ELSE
2196 0 : CPABORT("Quadrupole oscillator strengths only for singlet and spin-conserving excitations")
2197 : END IF
2198 0 : ndo_mo = donor_state%ndo_mo
2199 0 : ndo_so = ndo_mo*nspins
2200 0 : ngs = ndo_so; IF (xas_tdp_control%do_roks) ngs = ndo_mo !only alpha do_mo in ROKS
2201 0 : nosc = SIZE(lr_evals)
2202 0 : ALLOCATE (donor_state%quad_osc_str(nosc))
2203 0 : osc_str => donor_state%quad_osc_str
2204 0 : osc_str = 0.0_dp
2205 0 : quadmat => xas_tdp_env%quadmat
2206 :
2207 : !work matrices init
2208 : CALL cp_fm_get_info(donor_state%gs_coeffs, matrix_struct=col_struct, para_env=para_env, &
2209 0 : context=blacs_env, nrow_global=nao)
2210 : CALL cp_fm_struct_create(mat_struct, para_env=para_env, context=blacs_env, &
2211 0 : nrow_global=ndo_so*nosc, ncol_global=ngs)
2212 0 : CALL cp_fm_create(mat_work, mat_struct)
2213 0 : CALL cp_fm_create(col_work, col_struct)
2214 :
2215 0 : ALLOCATE (quad_block(ndo_so, ngs), tot_contr(ndo_mo))
2216 0 : pref = 2.0_dp; IF (do_sc) pref = 1.0_dp !because of singlet definition u = 1/sqrt(2)*...
2217 0 : ALLOCATE (trace(nosc))
2218 0 : trace = 0.0_dp
2219 :
2220 : !Loop over the cartesioan coord :x2, xy, xz, y2, yz, z2
2221 0 : DO j = 1, 6
2222 :
2223 : !Compute quad*gs_coeffs
2224 0 : CALL cp_dbcsr_sm_fm_multiply(quadmat(j)%matrix, donor_state%gs_coeffs, col_work, ncol=ngs)
2225 : !compute lr_coeffs*quadmat*gs_coeffs
2226 0 : CALL parallel_gemm('T', 'N', ndo_so*nosc, ngs, nao, 1.0_dp, lr_coeffs, col_work, 0.0_dp, mat_work)
2227 :
2228 : !Loop over the excited states
2229 0 : DO iosc = 1, nosc
2230 :
2231 0 : tot_contr = 0.0_dp
2232 : CALL cp_fm_get_submatrix(fm=mat_work, target_m=quad_block, start_row=(iosc - 1)*ndo_so + 1, &
2233 0 : start_col=1, n_rows=ndo_so, n_cols=ngs)
2234 :
2235 0 : IF (do_sg) THEN
2236 0 : tot_contr(:) = get_diag(quad_block)
2237 0 : ELSE IF (do_sc .AND. xas_tdp_control%do_uks) THEN
2238 0 : tot_contr(:) = get_diag(quad_block(1:ndo_mo, 1:ndo_mo)) !alpha
2239 0 : tot_contr(:) = tot_contr(:) + get_diag(quad_block(ndo_mo + 1:ndo_so, ndo_mo + 1:ndo_so)) !beta
2240 : ELSE
2241 : !roks
2242 0 : tot_contr(:) = get_diag(quad_block(1:ndo_mo, :)) !alpha
2243 0 : tot_contr(:) = tot_contr(:) + get_diag(quad_block(ndo_mo + 1:ndo_so, :)) !beta
2244 : END IF
2245 :
2246 : !if x2, y2, or z2 direction, need to update the trace (for later)
2247 0 : IF (j == 1 .OR. j == 4 .OR. j == 6) THEN
2248 0 : osc_str(iosc) = osc_str(iosc) + SUM(tot_contr)**2
2249 0 : trace(iosc) = trace(iosc) + SUM(tot_contr)
2250 :
2251 : !if xy, xz or yz, need to count twice the contribution (for yx, zx and zy)
2252 : ELSE
2253 0 : osc_str(iosc) = osc_str(iosc) + 2.0_dp*SUM(tot_contr)**2
2254 : END IF
2255 :
2256 : END DO !iosc
2257 : END DO !j
2258 :
2259 : !compute the prefactor, and remove 1/3*trace^2
2260 0 : osc_str(:) = pref*1._dp/20._dp*a_fine**2*lr_evals(:)**3*(osc_str(:) - 1._dp/3._dp*trace(:)**2)
2261 :
2262 : !clean-up
2263 0 : CALL cp_fm_release(mat_work)
2264 0 : CALL cp_fm_release(col_work)
2265 0 : CALL cp_fm_struct_release(mat_struct)
2266 :
2267 0 : CALL timestop(handle)
2268 :
2269 0 : END SUBROUTINE compute_quadrupole_fosc
2270 :
2271 : ! **************************************************************************************************
2272 : !> \brief Writes the core MOs to excited atoms associations in the main output file
2273 : !> \param xas_tdp_env ...
2274 : !> \param xas_tdp_control ...
2275 : !> \param qs_env ...
2276 : !> \note Look at alpha spin MOs, as we are dealing with core states and alpha/beta MOs are the same
2277 : ! **************************************************************************************************
2278 48 : SUBROUTINE write_mos_to_ex_atoms_association(xas_tdp_env, xas_tdp_control, qs_env)
2279 :
2280 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2281 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2282 : TYPE(qs_environment_type), POINTER :: qs_env
2283 :
2284 : CHARACTER(LEN=default_string_length) :: kind_name
2285 : INTEGER :: at_index, imo, ispin, nmo, nspins, &
2286 : output_unit, tmp_index
2287 : INTEGER, DIMENSION(3) :: perd_init
2288 48 : INTEGER, DIMENSION(:), POINTER :: ex_atom_indices
2289 48 : INTEGER, DIMENSION(:, :, :), POINTER :: mos_of_ex_atoms
2290 : REAL(dp) :: dist, mo_spread
2291 : REAL(dp), DIMENSION(3) :: at_pos, r_ac, wfn_center
2292 : TYPE(cell_type), POINTER :: cell
2293 48 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
2294 :
2295 48 : NULLIFY (cell, particle_set, mos_of_ex_atoms, ex_atom_indices)
2296 :
2297 96 : output_unit = cp_logger_get_default_io_unit()
2298 :
2299 48 : IF (output_unit > 0) THEN
2300 : WRITE (UNIT=output_unit, FMT="(/,T3,A,/,T3,A,/,T3,A)") &
2301 24 : " Associated Associated Distance to MO spread (Ang^2)", &
2302 24 : "Spin MO index atom index atom kind MO center (Ang) -w_i ln(|z_ij|^2)", &
2303 48 : "---------------------------------------------------------------------------------"
2304 : END IF
2305 :
2306 : ! Initialization
2307 48 : nspins = 1; IF (xas_tdp_control%do_uks) nspins = 2
2308 48 : mos_of_ex_atoms => xas_tdp_env%mos_of_ex_atoms
2309 48 : ex_atom_indices => xas_tdp_env%ex_atom_indices
2310 48 : nmo = xas_tdp_control%n_search
2311 48 : CALL get_qs_env(qs_env=qs_env, particle_set=particle_set, cell=cell)
2312 :
2313 : ! because the use of Berry's phase operator implies PBCs
2314 192 : perd_init = cell%perd
2315 192 : cell%perd = 1
2316 :
2317 : ! Retrieving all the info for each MO and spin
2318 304 : DO imo = 1, nmo
2319 576 : DO ispin = 1, nspins
2320 :
2321 : ! each Mo is associated to at most one atom (only 1 in array of -1)
2322 758 : IF (ANY(mos_of_ex_atoms(imo, :, ispin) == 1)) THEN
2323 252 : tmp_index = MAXLOC(mos_of_ex_atoms(imo, :, ispin), 1)
2324 114 : at_index = ex_atom_indices(tmp_index)
2325 114 : kind_name = particle_set(at_index)%atomic_kind%name
2326 :
2327 456 : at_pos = particle_set(at_index)%r
2328 456 : wfn_center = xas_tdp_env%qs_loc_env%localized_wfn_control%centers_set(ispin)%array(1:3, imo)
2329 114 : r_ac = pbc(at_pos, wfn_center, cell)
2330 456 : dist = NORM2(r_ac)
2331 : ! convert distance from a.u. to Angstrom
2332 114 : dist = dist*angstrom
2333 :
2334 114 : mo_spread = xas_tdp_env%qs_loc_env%localized_wfn_control%centers_set(ispin)%array(4, imo)
2335 114 : mo_spread = mo_spread*angstrom*angstrom
2336 :
2337 114 : IF (output_unit > 0) THEN
2338 : WRITE (UNIT=output_unit, FMT="(T3,I4,I10,I14,A14,ES19.3,ES20.3)") &
2339 57 : ispin, imo, at_index, TRIM(kind_name), dist, mo_spread
2340 : END IF
2341 :
2342 : END IF
2343 : END DO !ispin
2344 : END DO !imo
2345 :
2346 48 : IF (output_unit > 0) THEN
2347 : WRITE (UNIT=output_unit, FMT="(T3,A,/)") &
2348 24 : "---------------------------------------------------------------------------------"
2349 : END IF
2350 :
2351 : ! Go back to initial BCs
2352 192 : cell%perd = perd_init
2353 :
2354 48 : END SUBROUTINE write_mos_to_ex_atoms_association
2355 :
2356 : ! **************************************************************************************************
2357 : !> \brief Performs Mulliken population analysis for the MO(s) of a donor_state_type so that user
2358 : !> can verify it is indeed a core state
2359 : !> \param donor_state ...
2360 : !> \param qs_env ...
2361 : !> \note This is a specific case of Mulliken analysis. In general one computes sum_i (SP)_ii, where
2362 : !> i labels the basis function centered on the atom of interest. For a specific MO with index
2363 : !> j, one need to compute sum_{ik} c_{ij} S_{ik} c_{kj}, k = 1,nao
2364 : ! **************************************************************************************************
2365 68 : SUBROUTINE perform_mulliken_on_donor_state(donor_state, qs_env)
2366 : TYPE(donor_state_type), POINTER :: donor_state
2367 : TYPE(qs_environment_type), POINTER :: qs_env
2368 :
2369 : INTEGER :: at_index, i, ispin, nao, natom, ndo_mo, &
2370 : ndo_so, nsgf, nspins, output_unit
2371 68 : INTEGER, DIMENSION(:), POINTER :: first_sgf, last_sgf
2372 68 : INTEGER, DIMENSION(:, :), POINTER :: mo_indices
2373 68 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: mul_pop, pop_mat
2374 68 : REAL(dp), DIMENSION(:, :), POINTER :: work_array
2375 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2376 : TYPE(cp_fm_struct_type), POINTER :: col_vect_struct
2377 : TYPE(cp_fm_type) :: work_vect
2378 : TYPE(cp_fm_type), POINTER :: gs_coeffs
2379 68 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_s
2380 : TYPE(mp_para_env_type), POINTER :: para_env
2381 68 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
2382 68 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
2383 :
2384 68 : NULLIFY (mo_indices, qs_kind_set, particle_set, first_sgf, work_array)
2385 68 : NULLIFY (matrix_s, para_env, blacs_env, col_vect_struct, last_sgf)
2386 :
2387 : ! Initialization
2388 68 : at_index = donor_state%at_index
2389 68 : mo_indices => donor_state%mo_indices
2390 68 : ndo_mo = donor_state%ndo_mo
2391 68 : gs_coeffs => donor_state%gs_coeffs
2392 136 : output_unit = cp_logger_get_default_io_unit()
2393 68 : nspins = 1; IF (SIZE(mo_indices, 2) == 2) nspins = 2
2394 68 : ndo_so = ndo_mo*nspins
2395 272 : ALLOCATE (mul_pop(ndo_mo, nspins))
2396 240 : mul_pop = 0.0_dp
2397 :
2398 : CALL get_qs_env(qs_env=qs_env, particle_set=particle_set, qs_kind_set=qs_kind_set, &
2399 68 : para_env=para_env, blacs_env=blacs_env, matrix_s=matrix_s)
2400 68 : CALL cp_fm_get_info(gs_coeffs, nrow_global=nao, matrix_struct=col_vect_struct)
2401 :
2402 68 : natom = SIZE(particle_set, 1)
2403 204 : ALLOCATE (first_sgf(natom))
2404 204 : ALLOCATE (last_sgf(natom))
2405 :
2406 68 : CALL get_particle_set(particle_set, qs_kind_set, first_sgf=first_sgf, last_sgf=last_sgf)
2407 68 : nsgf = last_sgf(at_index) - first_sgf(at_index) + 1
2408 :
2409 68 : CALL cp_fm_create(work_vect, col_vect_struct)
2410 :
2411 : ! Take the product of S*coeffs
2412 68 : CALL cp_dbcsr_sm_fm_multiply(matrix_s(1)%matrix, gs_coeffs, work_vect, ncol=ndo_so)
2413 :
2414 : ! Only consider the product coeffs^T * S * coeffs on the atom of interest
2415 272 : ALLOCATE (work_array(nsgf, ndo_so))
2416 272 : ALLOCATE (pop_mat(ndo_so, ndo_so))
2417 :
2418 : CALL cp_fm_get_submatrix(fm=work_vect, target_m=work_array, start_row=first_sgf(at_index), &
2419 68 : start_col=1, n_rows=nsgf, n_cols=ndo_so, transpose=.FALSE.)
2420 :
2421 : CALL dgemm('T', 'N', ndo_so, ndo_so, nsgf, 1.0_dp, donor_state%contract_coeffs, nsgf, &
2422 68 : work_array, nsgf, 0.0_dp, pop_mat, ndo_so)
2423 :
2424 : ! The Mullikan population for the MOs in on the diagonal.
2425 144 : DO ispin = 1, nspins
2426 240 : DO i = 1, ndo_mo
2427 172 : mul_pop(i, ispin) = pop_mat((ispin - 1)*ndo_mo + i, (ispin - 1)*ndo_mo + i)
2428 : END DO
2429 : END DO
2430 :
2431 : ! Printing in main output file
2432 68 : IF (output_unit > 0) THEN
2433 : WRITE (UNIT=output_unit, FMT="(T5,A,/,T5,A)") &
2434 34 : "Mulliken population analysis retricted to the associated MO(s) yields: ", &
2435 68 : " Spin MO index charge"
2436 72 : DO ispin = 1, nspins
2437 120 : DO i = 1, ndo_mo
2438 : WRITE (UNIT=output_unit, FMT="(T51,I4,I10,F11.3)") &
2439 86 : ispin, mo_indices(i, ispin), mul_pop(i, ispin)
2440 : END DO
2441 : END DO
2442 : END IF
2443 :
2444 : ! Clean-up
2445 68 : DEALLOCATE (first_sgf, last_sgf, work_array)
2446 68 : CALL cp_fm_release(work_vect)
2447 :
2448 204 : END SUBROUTINE perform_mulliken_on_donor_state
2449 :
2450 : ! **************************************************************************************************
2451 : !> \brief write the PDOS wrt the LR-orbitals for the current donor_state and/or the CUBES files
2452 : !> \param ex_type the excitation type: singlet, triplet, spin-conserving, etc
2453 : !> \param donor_state ...
2454 : !> \param xas_tdp_env ...
2455 : !> \param xas_tdp_section ...
2456 : !> \param qs_env ...
2457 : ! **************************************************************************************************
2458 70 : SUBROUTINE xas_tdp_post(ex_type, donor_state, xas_tdp_env, xas_tdp_section, qs_env)
2459 :
2460 : INTEGER, INTENT(IN) :: ex_type
2461 : TYPE(donor_state_type), POINTER :: donor_state
2462 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2463 : TYPE(section_vals_type), POINTER :: xas_tdp_section
2464 : TYPE(qs_environment_type), POINTER :: qs_env
2465 :
2466 : CHARACTER(len=*), PARAMETER :: routineN = 'xas_tdp_post'
2467 :
2468 : CHARACTER(len=default_string_length) :: domo, domon, excite, pos, xas_mittle
2469 : INTEGER :: ex_state_idx, handle, ic, ido_mo, imo, irep, ispin, n_dependent, n_rep, nao, &
2470 : ncubes, ndo_mo, ndo_so, nlumo, nmo, nspins, output_unit
2471 62 : INTEGER, DIMENSION(:), POINTER :: bounds, list, state_list
2472 : LOGICAL :: append_cube, do_cubes, do_pdos, &
2473 : do_wfn_restart
2474 62 : REAL(dp), DIMENSION(:), POINTER :: lr_evals
2475 62 : REAL(dp), DIMENSION(:, :), POINTER :: centers
2476 62 : TYPE(atomic_kind_type), DIMENSION(:), POINTER :: atomic_kind_set
2477 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2478 : TYPE(cp_fm_struct_type), POINTER :: fm_struct, mo_struct
2479 : TYPE(cp_fm_type) :: mo_coeff, work_fm
2480 : TYPE(cp_fm_type), POINTER :: lr_coeffs
2481 : TYPE(cp_logger_type), POINTER :: logger
2482 62 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_s
2483 62 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
2484 : TYPE(mo_set_type), POINTER :: mo_set
2485 : TYPE(mp_para_env_type), POINTER :: para_env
2486 62 : TYPE(particle_type), DIMENSION(:), POINTER :: particle_set
2487 62 : TYPE(qs_kind_type), DIMENSION(:), POINTER :: qs_kind_set
2488 : TYPE(section_vals_type), POINTER :: print_key
2489 :
2490 62 : NULLIFY (atomic_kind_set, particle_set, qs_kind_set, mo_set, lr_evals, lr_coeffs)
2491 62 : NULLIFY (mo_struct, para_env, blacs_env, fm_struct, matrix_s, print_key, logger)
2492 62 : NULLIFY (bounds, state_list, list, mos)
2493 :
2494 : !Tests on what to do
2495 124 : logger => cp_get_default_logger()
2496 62 : do_pdos = .FALSE.; do_cubes = .FALSE.; do_wfn_restart = .FALSE.
2497 :
2498 62 : IF (BTEST(cp_print_key_should_output(logger%iter_info, xas_tdp_section, &
2499 2 : "PRINT%PDOS"), cp_p_file)) do_pdos = .TRUE.
2500 :
2501 62 : IF (BTEST(cp_print_key_should_output(logger%iter_info, xas_tdp_section, &
2502 2 : "PRINT%CUBES"), cp_p_file)) do_cubes = .TRUE.
2503 :
2504 62 : IF (BTEST(cp_print_key_should_output(logger%iter_info, xas_tdp_section, &
2505 2 : "PRINT%RESTART_WFN"), cp_p_file)) do_wfn_restart = .TRUE.
2506 :
2507 62 : IF (.NOT. (do_pdos .OR. do_cubes .OR. do_wfn_restart)) RETURN
2508 :
2509 4 : CALL timeset(routineN, handle)
2510 :
2511 : !Initialization
2512 : CALL get_qs_env(qs_env, atomic_kind_set=atomic_kind_set, particle_set=particle_set, &
2513 : qs_kind_set=qs_kind_set, para_env=para_env, blacs_env=blacs_env, &
2514 4 : matrix_s=matrix_s, mos=mos)
2515 :
2516 4 : SELECT CASE (ex_type)
2517 : CASE (tddfpt_spin_cons)
2518 0 : lr_evals => donor_state%sc_evals
2519 0 : lr_coeffs => donor_state%sc_coeffs
2520 0 : nspins = 2
2521 0 : excite = "spincons"
2522 : CASE (tddfpt_spin_flip)
2523 0 : lr_evals => donor_state%sf_evals
2524 0 : lr_coeffs => donor_state%sf_coeffs
2525 0 : nspins = 2
2526 0 : excite = "spinflip"
2527 : CASE (tddfpt_singlet)
2528 4 : lr_evals => donor_state%sg_evals
2529 4 : lr_coeffs => donor_state%sg_coeffs
2530 4 : nspins = 1
2531 4 : excite = "singlet"
2532 : CASE (tddfpt_triplet)
2533 0 : lr_evals => donor_state%tp_evals
2534 0 : lr_coeffs => donor_state%tp_coeffs
2535 0 : nspins = 1
2536 4 : excite = "triplet"
2537 : END SELECT
2538 :
2539 8 : SELECT CASE (donor_state%state_type)
2540 : CASE (xas_1s_type)
2541 4 : domo = "1s"
2542 : CASE (xas_2s_type)
2543 0 : domo = "2s"
2544 : CASE (xas_2p_type)
2545 4 : domo = "2p"
2546 : END SELECT
2547 :
2548 4 : ndo_mo = donor_state%ndo_mo
2549 4 : ndo_so = ndo_mo*nspins
2550 4 : nmo = SIZE(lr_evals)
2551 4 : CALL dbcsr_get_info(matrix_s(1)%matrix, nfullrows_total=nao)
2552 :
2553 : CALL cp_fm_struct_create(mo_struct, context=blacs_env, para_env=para_env, &
2554 4 : nrow_global=nao, ncol_global=nmo)
2555 4 : CALL cp_fm_create(mo_coeff, mo_struct)
2556 :
2557 : !Dump the TDDFT excited state AMEW wavefunction into a file for restart in RTP
2558 4 : IF (do_wfn_restart) THEN
2559 2 : BLOCK
2560 6 : TYPE(mo_set_type), DIMENSION(2) :: restart_mos
2561 2 : IF (.NOT. (nspins == 1 .AND. donor_state%state_type == xas_1s_type)) THEN
2562 0 : CPABORT("RESTART.wfn file only available for RKS K-edge XAS spectroscopy")
2563 : END IF
2564 :
2565 2 : CALL section_vals_val_get(xas_tdp_section, "PRINT%RESTART_WFN%EXCITED_STATE_INDEX", n_rep_val=n_rep)
2566 :
2567 4 : DO irep = 1, n_rep
2568 : CALL section_vals_val_get(xas_tdp_section, "PRINT%RESTART_WFN%EXCITED_STATE_INDEX", &
2569 2 : i_rep_val=irep, i_val=ex_state_idx)
2570 2 : CPASSERT(ex_state_idx <= SIZE(lr_evals))
2571 :
2572 6 : DO ispin = 1, 2
2573 4 : CALL duplicate_mo_set(restart_mos(ispin), mos(1))
2574 : ! Set the new occupation number in the case of spin-independent based calculaltion since the restart is spin-depedent
2575 4 : IF (SIZE(mos) == 1) &
2576 26 : restart_mos(ispin)%occupation_numbers = mos(1)%occupation_numbers/2
2577 : END DO
2578 :
2579 : CALL cp_fm_to_fm_submat(msource=lr_coeffs, mtarget=restart_mos(1)%mo_coeff, nrow=nao, &
2580 : ncol=1, s_firstrow=1, s_firstcol=ex_state_idx, t_firstrow=1, &
2581 2 : t_firstcol=donor_state%mo_indices(1, 1))
2582 :
2583 : xas_mittle = 'xasat'//TRIM(ADJUSTL(cp_to_string(donor_state%at_index)))//'_'//TRIM(domo)// &
2584 2 : '_'//TRIM(excite)//'_idx'//TRIM(ADJUSTL(cp_to_string(ex_state_idx)))
2585 : output_unit = cp_print_key_unit_nr(logger, xas_tdp_section, "PRINT%RESTART_WFN", &
2586 : extension=".wfn", file_status="REPLACE", &
2587 : file_action="WRITE", file_form="UNFORMATTED", &
2588 2 : middle_name=xas_mittle)
2589 :
2590 : CALL write_mo_set_low(restart_mos, particle_set=particle_set, &
2591 2 : qs_kind_set=qs_kind_set, ires=output_unit)
2592 :
2593 2 : CALL cp_print_key_finished_output(output_unit, logger, xas_tdp_section, "PRINT%RESTART_WFN")
2594 :
2595 10 : DO ispin = 1, 2
2596 6 : CALL deallocate_mo_set(restart_mos(ispin))
2597 : END DO
2598 : END DO
2599 : END BLOCK
2600 : END IF
2601 :
2602 : !PDOS related stuff
2603 4 : IF (do_pdos) THEN
2604 :
2605 : !If S^0.5 not yet stored, compute it once and for all
2606 2 : IF (.NOT. ASSOCIATED(xas_tdp_env%matrix_shalf) .AND. do_pdos) THEN
2607 : CALL cp_fm_struct_create(fm_struct, context=blacs_env, para_env=para_env, &
2608 2 : nrow_global=nao, ncol_global=nao)
2609 2 : ALLOCATE (xas_tdp_env%matrix_shalf)
2610 2 : CALL cp_fm_create(xas_tdp_env%matrix_shalf, fm_struct)
2611 2 : CALL cp_fm_create(work_fm, fm_struct)
2612 :
2613 2 : CALL copy_dbcsr_to_fm(matrix_s(1)%matrix, xas_tdp_env%matrix_shalf)
2614 2 : CALL cp_fm_power(xas_tdp_env%matrix_shalf, work_fm, 0.5_dp, EPSILON(0.0_dp), n_dependent)
2615 :
2616 2 : CALL cp_fm_release(work_fm)
2617 2 : CALL cp_fm_struct_release(fm_struct)
2618 : END IF
2619 :
2620 : !Giving some PDOS info
2621 2 : output_unit = cp_logger_get_default_io_unit()
2622 2 : IF (output_unit > 0) THEN
2623 : WRITE (UNIT=output_unit, FMT="(/,T5,A,/,T5,A,/,T5,A)") &
2624 1 : "Computing the PDOS of linear-response orbitals for spectral features analysis", &
2625 1 : "Note: using standard PDOS routines => ignore mentions of KS states and MO ", &
2626 2 : " occupation numbers. Eigenvalues in *.pdos files are excitations energies."
2627 : END IF
2628 :
2629 : !Check on NLUMO
2630 2 : CALL section_vals_val_get(xas_tdp_section, "PRINT%PDOS%NLUMO", i_val=nlumo)
2631 2 : IF (nlumo .NE. 0) THEN
2632 0 : CPWARN("NLUMO is irrelevant for XAS_TDP PDOS. It was overwritten to 0.")
2633 : END IF
2634 2 : CALL section_vals_val_set(xas_tdp_section, "PRINT%PDOS%NLUMO", i_val=0)
2635 : END IF
2636 :
2637 : !CUBES related stuff
2638 4 : IF (do_cubes) THEN
2639 :
2640 2 : print_key => section_vals_get_subs_vals(xas_tdp_section, "PRINT%CUBES")
2641 :
2642 2 : CALL section_vals_val_get(print_key, "CUBES_LU_BOUNDS", i_vals=bounds)
2643 2 : ncubes = bounds(2) - bounds(1) + 1
2644 2 : IF (ncubes > 0) THEN
2645 0 : ALLOCATE (state_list(ncubes))
2646 0 : DO ic = 1, ncubes
2647 0 : state_list(ic) = bounds(1) + ic - 1
2648 : END DO
2649 : END IF
2650 :
2651 2 : IF (.NOT. ASSOCIATED(state_list)) THEN
2652 2 : CALL section_vals_val_get(print_key, "CUBES_LIST", n_rep_val=n_rep)
2653 :
2654 2 : ncubes = 0
2655 4 : DO irep = 1, n_rep
2656 2 : NULLIFY (list)
2657 2 : CALL section_vals_val_get(print_key, "CUBES_LIST", i_rep_val=irep, i_vals=list)
2658 4 : IF (ASSOCIATED(list)) THEN
2659 2 : CALL reallocate(state_list, 1, ncubes + SIZE(list))
2660 4 : DO ic = 1, SIZE(list)
2661 4 : state_list(ncubes + ic) = list(ic)
2662 : END DO
2663 2 : ncubes = ncubes + SIZE(list)
2664 : END IF
2665 : END DO
2666 : END IF
2667 :
2668 2 : IF (.NOT. ASSOCIATED(state_list)) THEN
2669 0 : ncubes = 1
2670 0 : ALLOCATE (state_list(1))
2671 0 : state_list(1) = 1
2672 : END IF
2673 :
2674 2 : CALL section_vals_val_get(print_key, "APPEND", l_val=append_cube)
2675 2 : pos = "REWIND"
2676 2 : IF (append_cube) pos = "APPEND"
2677 :
2678 6 : ALLOCATE (centers(6, ncubes))
2679 18 : centers = 0.0_dp
2680 :
2681 : END IF
2682 :
2683 : !Loop over MOs and spin, one PDOS/CUBE for each
2684 8 : DO ido_mo = 1, ndo_mo
2685 12 : DO ispin = 1, nspins
2686 :
2687 : !need to create a mo set for the LR-orbitals
2688 4 : ALLOCATE (mo_set)
2689 : CALL allocate_mo_set(mo_set, nao=nao, nmo=nmo, nelectron=nmo, n_el_f=REAL(nmo, dp), &
2690 4 : maxocc=1.0_dp, flexible_electron_count=0.0_dp)
2691 4 : CALL init_mo_set(mo_set, fm_ref=mo_coeff, name="PDOS XAS_TDP MOs")
2692 156 : mo_set%eigenvalues(:) = lr_evals(:)
2693 :
2694 : !get the actual coeff => most common case: closed-shell K-edge, can directly take lr_coeffs
2695 4 : IF (nspins == 1 .AND. ndo_mo == 1) THEN
2696 4 : CALL cp_fm_to_fm(lr_coeffs, mo_set%mo_coeff)
2697 : ELSE
2698 0 : DO imo = 1, nmo
2699 : CALL cp_fm_to_fm_submat(msource=lr_coeffs, mtarget=mo_set%mo_coeff, &
2700 : nrow=nao, ncol=1, s_firstrow=1, &
2701 : s_firstcol=(imo - 1)*ndo_so + (ispin - 1)*ndo_mo + ido_mo, &
2702 0 : t_firstrow=1, t_firstcol=imo)
2703 : END DO
2704 : END IF
2705 :
2706 : !naming the output
2707 4 : domon = domo
2708 4 : IF (donor_state%state_type == xas_2p_type) domon = TRIM(domo)//TRIM(ADJUSTL(cp_to_string(ido_mo)))
2709 : xas_mittle = 'xasat'//TRIM(ADJUSTL(cp_to_string(donor_state%at_index)))//'_'// &
2710 4 : TRIM(domon)//'_'//TRIM(excite)
2711 :
2712 4 : IF (do_pdos) THEN
2713 : CALL calculate_projected_dos(mo_set, atomic_kind_set, qs_kind_set, particle_set, &
2714 : qs_env, xas_tdp_section, ispin, xas_mittle, &
2715 2 : external_matrix_shalf=xas_tdp_env%matrix_shalf)
2716 : END IF
2717 :
2718 4 : IF (do_cubes) THEN
2719 : CALL qs_print_cubes(qs_env, mo_set%mo_coeff, ncubes, state_list, centers, &
2720 : print_key=print_key, root=xas_mittle, ispin=ispin, &
2721 2 : file_position=pos)
2722 : END IF
2723 :
2724 : !clean-up
2725 4 : CALL deallocate_mo_set(mo_set)
2726 8 : DEALLOCATE (mo_set)
2727 :
2728 : END DO
2729 : END DO
2730 :
2731 : !clean-up
2732 4 : CALL cp_fm_release(mo_coeff)
2733 4 : CALL cp_fm_struct_release(mo_struct)
2734 4 : IF (do_cubes) DEALLOCATE (centers, state_list)
2735 :
2736 4 : CALL timestop(handle)
2737 :
2738 62 : END SUBROUTINE xas_tdp_post
2739 :
2740 : ! **************************************************************************************************
2741 : !> \brief Computed the LUMOs for the OT eigensolver guesses
2742 : !> \param xas_tdp_env ...
2743 : !> \param xas_tdp_control ...
2744 : !> \param qs_env ...
2745 : !> \note Uses stendard diagonalization. Do not use the stendard make_lumo subroutine as it uses
2746 : !> the OT eigensolver and there is no guarantee that it will converge fast
2747 : ! **************************************************************************************************
2748 20 : SUBROUTINE make_lumo_guess(xas_tdp_env, xas_tdp_control, qs_env)
2749 :
2750 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2751 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2752 : TYPE(qs_environment_type), POINTER :: qs_env
2753 :
2754 : CHARACTER(len=*), PARAMETER :: routineN = 'make_lumo_guess'
2755 :
2756 : INTEGER :: handle, ispin, nao, nelec_spin(2), &
2757 : nlumo(2), nocc(2), nspins
2758 : LOGICAL :: do_os
2759 20 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: evals
2760 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
2761 : TYPE(cp_fm_struct_type), POINTER :: fm_struct, lumo_struct
2762 : TYPE(cp_fm_type) :: amatrix, bmatrix, evecs, work_fm
2763 20 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_ks, matrix_s
2764 : TYPE(mp_para_env_type), POINTER :: para_env
2765 :
2766 20 : NULLIFY (matrix_ks, matrix_s, para_env, blacs_env)
2767 20 : NULLIFY (lumo_struct, fm_struct)
2768 :
2769 20 : CALL timeset(routineN, handle)
2770 :
2771 20 : do_os = xas_tdp_control%do_uks .OR. xas_tdp_control%do_roks
2772 2 : nspins = 1; IF (do_os) nspins = 2
2773 82 : ALLOCATE (xas_tdp_env%lumo_evecs(nspins))
2774 82 : ALLOCATE (xas_tdp_env%lumo_evals(nspins))
2775 : CALL get_qs_env(qs_env, matrix_ks=matrix_ks, matrix_s=matrix_s, nelectron_spin=nelec_spin, &
2776 20 : para_env=para_env, blacs_env=blacs_env)
2777 20 : CALL dbcsr_get_info(matrix_s(1)%matrix, nfullrows_total=nao)
2778 :
2779 20 : IF (do_os) THEN
2780 6 : nlumo = nao - nelec_spin
2781 2 : nocc = nelec_spin
2782 : ELSE
2783 54 : nlumo = nao - nelec_spin(1)/2
2784 54 : nocc = nelec_spin(1)/2
2785 : END IF
2786 :
2787 82 : ALLOCATE (xas_tdp_env%ot_prec(nspins))
2788 :
2789 42 : DO ispin = 1, nspins
2790 :
2791 : !Going through fm to diagonalize
2792 : CALL cp_fm_struct_create(fm_struct, para_env=para_env, context=blacs_env, &
2793 22 : nrow_global=nao, ncol_global=nao)
2794 22 : CALL cp_fm_create(amatrix, fm_struct)
2795 22 : CALL cp_fm_create(bmatrix, fm_struct)
2796 22 : CALL cp_fm_create(evecs, fm_struct)
2797 22 : CALL cp_fm_create(work_fm, fm_struct)
2798 66 : ALLOCATE (evals(nao))
2799 66 : ALLOCATE (xas_tdp_env%lumo_evals(ispin)%array(nlumo(ispin)))
2800 :
2801 22 : CALL copy_dbcsr_to_fm(matrix_ks(ispin)%matrix, amatrix)
2802 22 : CALL copy_dbcsr_to_fm(matrix_s(1)%matrix, bmatrix)
2803 :
2804 : !The actual diagonalization through Cholesky decomposition
2805 22 : CALL cp_fm_geeig(amatrix, bmatrix, evecs, evals, work_fm)
2806 :
2807 : !Storing results
2808 : CALL cp_fm_struct_create(lumo_struct, para_env=para_env, context=blacs_env, &
2809 22 : nrow_global=nao, ncol_global=nlumo(ispin))
2810 22 : CALL cp_fm_create(xas_tdp_env%lumo_evecs(ispin), lumo_struct)
2811 :
2812 : CALL cp_fm_to_fm_submat(evecs, xas_tdp_env%lumo_evecs(ispin), nrow=nao, &
2813 : ncol=nlumo(ispin), s_firstrow=1, s_firstcol=nocc(ispin) + 1, &
2814 22 : t_firstrow=1, t_firstcol=1)
2815 :
2816 1098 : xas_tdp_env%lumo_evals(ispin)%array(1:nlumo(ispin)) = evals(nocc(ispin) + 1:nao)
2817 :
2818 22 : CALL build_ot_spin_prec(evecs, evals, ispin, xas_tdp_env, xas_tdp_control, qs_env)
2819 :
2820 : !clean-up
2821 22 : CALL cp_fm_release(amatrix)
2822 22 : CALL cp_fm_release(bmatrix)
2823 22 : CALL cp_fm_release(evecs)
2824 22 : CALL cp_fm_release(work_fm)
2825 22 : CALL cp_fm_struct_release(fm_struct)
2826 22 : CALL cp_fm_struct_release(lumo_struct)
2827 42 : DEALLOCATE (evals)
2828 : END DO
2829 :
2830 20 : CALL timestop(handle)
2831 :
2832 60 : END SUBROUTINE make_lumo_guess
2833 :
2834 : ! **************************************************************************************************
2835 : !> \brief Builds a preconditioner for the OT eigensolver, based on some heurstics that prioritize
2836 : !> LUMOs with lower eigenvalues
2837 : !> \param evecs all the ground state eigenvectors
2838 : !> \param evals all the ground state eigenvalues
2839 : !> \param ispin ...
2840 : !> \param xas_tdp_env ...
2841 : !> \param xas_tdp_control ...
2842 : !> \param qs_env ...
2843 : !> \note assumes that the preconditioner matrix array is allocated
2844 : ! **************************************************************************************************
2845 22 : SUBROUTINE build_ot_spin_prec(evecs, evals, ispin, xas_tdp_env, xas_tdp_control, qs_env)
2846 :
2847 : TYPE(cp_fm_type), INTENT(IN) :: evecs
2848 : REAL(dp), DIMENSION(:) :: evals
2849 : INTEGER :: ispin
2850 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2851 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2852 : TYPE(qs_environment_type), POINTER :: qs_env
2853 :
2854 : CHARACTER(len=*), PARAMETER :: routineN = 'build_ot_spin_prec'
2855 :
2856 : INTEGER :: handle, nao, nelec_spin(2), nguess, &
2857 : nocc, nspins
2858 : LOGICAL :: do_os
2859 : REAL(dp) :: shift
2860 : REAL(dp), ALLOCATABLE, DIMENSION(:) :: scaling
2861 : TYPE(cp_fm_struct_type), POINTER :: fm_struct
2862 : TYPE(cp_fm_type) :: fm_prec, work_fm
2863 22 : TYPE(dbcsr_p_type), DIMENSION(:), POINTER :: matrix_s
2864 : TYPE(mp_para_env_type), POINTER :: para_env
2865 :
2866 22 : NULLIFY (fm_struct, para_env, matrix_s)
2867 :
2868 22 : CALL timeset(routineN, handle)
2869 :
2870 22 : do_os = xas_tdp_control%do_uks .OR. xas_tdp_control%do_roks
2871 22 : CALL get_qs_env(qs_env, para_env=para_env, nelectron_spin=nelec_spin, matrix_s=matrix_s)
2872 22 : CALL cp_fm_get_info(evecs, nrow_global=nao, matrix_struct=fm_struct)
2873 22 : CALL cp_fm_create(fm_prec, fm_struct)
2874 66 : ALLOCATE (scaling(nao))
2875 22 : nocc = nelec_spin(1)/2
2876 22 : nspins = 1
2877 22 : IF (do_os) THEN
2878 4 : nocc = nelec_spin(ispin)
2879 4 : nspins = 2
2880 : END IF
2881 :
2882 : !rough estimate of the number of required evals
2883 22 : nguess = nao - nocc
2884 22 : IF (xas_tdp_control%n_excited > 0 .AND. xas_tdp_control%n_excited < nguess) THEN
2885 4 : nguess = xas_tdp_control%n_excited/nspins
2886 18 : ELSE IF (xas_tdp_control%e_range > 0.0_dp) THEN
2887 514 : nguess = COUNT(evals(nocc + 1:nao) - evals(nocc + 1) .LE. xas_tdp_control%e_range)
2888 : END IF
2889 :
2890 : !Give max weight to the first LUMOs
2891 540 : scaling(nocc + 1:nocc + nguess) = 100.0_dp
2892 : !Then gradually decrease weight
2893 22 : shift = evals(nocc + 1) - 0.01_dp
2894 602 : scaling(nocc + nguess:nao) = 1.0_dp/(evals(nocc + nguess:nao) - shift)
2895 : !HOMOs do not matter, but need well behaved matrix
2896 616 : scaling(1:nocc) = 1.0_dp
2897 :
2898 : !Building the precond as an fm
2899 22 : CALL cp_fm_create(work_fm, fm_struct)
2900 :
2901 22 : CALL cp_fm_copy_general(evecs, work_fm, para_env)
2902 22 : CALL cp_fm_column_scale(work_fm, scaling)
2903 :
2904 22 : CALL parallel_gemm('N', 'T', nao, nao, nao, 1.0_dp, work_fm, evecs, 0.0_dp, fm_prec)
2905 :
2906 : !Copy into dbcsr format
2907 22 : ALLOCATE (xas_tdp_env%ot_prec(ispin)%matrix)
2908 22 : CALL dbcsr_create(xas_tdp_env%ot_prec(ispin)%matrix, template=matrix_s(1)%matrix, name="OT_PREC")
2909 22 : CALL copy_fm_to_dbcsr(fm_prec, xas_tdp_env%ot_prec(ispin)%matrix)
2910 22 : CALL dbcsr_filter(xas_tdp_env%ot_prec(ispin)%matrix, xas_tdp_control%eps_filter)
2911 :
2912 22 : CALL cp_fm_release(work_fm)
2913 22 : CALL cp_fm_release(fm_prec)
2914 :
2915 22 : CALL timestop(handle)
2916 :
2917 66 : END SUBROUTINE build_ot_spin_prec
2918 :
2919 : ! **************************************************************************************************
2920 : !> \brief Prints GW2X corrected ionization potentials to main output file, including SOC splitting
2921 : !> \param donor_state ...
2922 : !> \param xas_tdp_env ...
2923 : !> \param xas_tdp_control ...
2924 : !> \param qs_env ...
2925 : ! **************************************************************************************************
2926 30 : SUBROUTINE print_xps(donor_state, xas_tdp_env, xas_tdp_control, qs_env)
2927 :
2928 : TYPE(donor_state_type), POINTER :: donor_state
2929 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2930 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2931 : TYPE(qs_environment_type), POINTER :: qs_env
2932 :
2933 : INTEGER :: ido_mo, ispin, nspins, output_unit
2934 30 : REAL(dp), ALLOCATABLE, DIMENSION(:, :) :: IPs, soc_shifts
2935 :
2936 30 : output_unit = cp_logger_get_default_io_unit()
2937 :
2938 30 : nspins = 1; IF (xas_tdp_control%do_uks .OR. xas_tdp_control%do_roks) nspins = 2
2939 :
2940 120 : ALLOCATE (IPs(SIZE(donor_state%gw2x_evals, 1), SIZE(donor_state%gw2x_evals, 2)))
2941 106 : IPs(:, :) = donor_state%gw2x_evals(:, :)
2942 :
2943 : !IPs in PBCs cannot be trusted because of a lack of a potential reference
2944 30 : IF (.NOT. xas_tdp_control%is_periodic) THEN
2945 :
2946 : !Apply SOC splitting
2947 26 : IF (donor_state%ndo_mo > 1) THEN
2948 : CALL get_soc_splitting(soc_shifts, donor_state, xas_tdp_env, xas_tdp_control, qs_env)
2949 20 : IPs(:, :) = IPs(:, :) + soc_shifts
2950 :
2951 4 : IF (output_unit > 0) THEN
2952 : WRITE (output_unit, FMT="(/,T5,A,F23.6)") &
2953 2 : "Ionization potentials for XPS (GW2X + SOC): ", -IPs(1, 1)*evolt
2954 :
2955 4 : DO ispin = 1, nspins
2956 10 : DO ido_mo = 1, donor_state%ndo_mo
2957 :
2958 6 : IF (ispin == 1 .AND. ido_mo == 1) CYCLE
2959 :
2960 : WRITE (output_unit, FMT="(T5,A,F23.6)") &
2961 8 : " ", -IPs(ido_mo, ispin)*evolt
2962 :
2963 : END DO
2964 : END DO
2965 : END IF
2966 :
2967 : ELSE
2968 :
2969 : ! No SOC, only 1 donor MO per spin
2970 22 : IF (output_unit > 0) THEN
2971 : WRITE (output_unit, FMT="(/,T5,A,F29.6)") &
2972 11 : "Ionization potentials for XPS (GW2X): ", -IPs(1, 1)*evolt
2973 :
2974 11 : IF (nspins == 2) THEN
2975 : WRITE (output_unit, FMT="(T5,A,F29.6)") &
2976 2 : " ", -IPs(1, 2)*evolt
2977 : END IF
2978 : END IF
2979 :
2980 : END IF
2981 : END IF
2982 :
2983 30 : END SUBROUTINE print_xps
2984 :
2985 : ! **************************************************************************************************
2986 : !> \brief Prints the excitation energies and the oscillator strengths for a given donor_state in a file
2987 : !> \param donor_state the donor_state to print
2988 : !> \param xas_tdp_env ...
2989 : !> \param xas_tdp_control ...
2990 : !> \param xas_tdp_section ...
2991 : ! **************************************************************************************************
2992 56 : SUBROUTINE print_xas_tdp_to_file(donor_state, xas_tdp_env, xas_tdp_control, xas_tdp_section)
2993 :
2994 : TYPE(donor_state_type), POINTER :: donor_state
2995 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
2996 : TYPE(xas_tdp_control_type), POINTER :: xas_tdp_control
2997 : TYPE(section_vals_type), POINTER :: xas_tdp_section
2998 :
2999 : INTEGER :: i, output_unit, xas_tdp_unit
3000 : TYPE(cp_logger_type), POINTER :: logger
3001 :
3002 56 : NULLIFY (logger)
3003 56 : logger => cp_get_default_logger()
3004 :
3005 : xas_tdp_unit = cp_print_key_unit_nr(logger, xas_tdp_section, "PRINT%SPECTRUM", &
3006 : extension=".spectrum", file_position="APPEND", &
3007 56 : file_action="WRITE", file_form="FORMATTED")
3008 :
3009 56 : output_unit = cp_logger_get_default_io_unit()
3010 :
3011 56 : IF (output_unit > 0) THEN
3012 : WRITE (output_unit, FMT="(/,T5,A,/)") &
3013 28 : "Calculations done: "
3014 : END IF
3015 :
3016 56 : IF (xas_tdp_control%do_spin_cons) THEN
3017 8 : IF (xas_tdp_unit > 0) THEN
3018 :
3019 : ! Printing the general donor state information
3020 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3021 4 : "==================================================================================", &
3022 4 : "XAS TDP open-shell spin-conserving (no SOC) excitations for DONOR STATE: ", &
3023 4 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3024 4 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3025 4 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3026 8 : "=================================================================================="
3027 :
3028 : ! Simply dump the excitation energies/ oscillator strength as they come
3029 :
3030 4 : IF (xas_tdp_control%do_quad) THEN
3031 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3032 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3033 0 : DO i = 1, SIZE(donor_state%sc_evals)
3034 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3035 0 : i, donor_state%sc_evals(i)*evolt, donor_state%osc_str(i, 4), &
3036 0 : donor_state%quad_osc_str(i)
3037 : END DO
3038 4 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3039 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3040 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3041 0 : DO i = 1, SIZE(donor_state%sc_evals)
3042 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3043 0 : i, donor_state%sc_evals(i)*evolt, donor_state%osc_str(i, 4), &
3044 0 : donor_state%osc_str(i, 1), donor_state%osc_str(i, 2), donor_state%osc_str(i, 3)
3045 : END DO
3046 : ELSE
3047 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3048 4 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3049 108 : DO i = 1, SIZE(donor_state%sc_evals)
3050 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3051 108 : i, donor_state%sc_evals(i)*evolt, donor_state%osc_str(i, 4)
3052 : END DO
3053 : END IF
3054 :
3055 4 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3056 : END IF !xas_tdp_unit > 0
3057 :
3058 8 : IF (output_unit > 0) THEN
3059 : WRITE (output_unit, FMT="(T5,A,F17.6)") &
3060 4 : "First spin-conserving XAS excitation energy (eV): ", donor_state%sc_evals(1)*evolt
3061 : END IF
3062 :
3063 : END IF ! do_spin_cons
3064 :
3065 56 : IF (xas_tdp_control%do_spin_flip) THEN
3066 2 : IF (xas_tdp_unit > 0) THEN
3067 :
3068 : ! Printing the general donor state information
3069 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3070 1 : "==================================================================================", &
3071 1 : "XAS TDP open-shell spin-flip (no SOC) excitations for DONOR STATE: ", &
3072 1 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3073 1 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3074 1 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3075 2 : "=================================================================================="
3076 :
3077 : ! Simply dump the excitation energies/ oscillator strength as they come
3078 :
3079 1 : IF (xas_tdp_control%do_quad) THEN
3080 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3081 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3082 0 : DO i = 1, SIZE(donor_state%sf_evals)
3083 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3084 0 : i, donor_state%sf_evals(i)*evolt, 0.0_dp, 0.0_dp !spin-forbidden !
3085 : END DO
3086 1 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3087 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3088 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3089 0 : DO i = 1, SIZE(donor_state%sf_evals)
3090 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3091 0 : i, donor_state%sf_evals(i)*evolt, 0.0_dp, 0.0_dp, 0.0_dp, 0.0_dp
3092 : END DO
3093 : ELSE
3094 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3095 1 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3096 13 : DO i = 1, SIZE(donor_state%sf_evals)
3097 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3098 13 : i, donor_state%sf_evals(i)*evolt, 0.0_dp
3099 : END DO
3100 : END IF
3101 :
3102 1 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3103 : END IF !xas_tdp_unit
3104 :
3105 2 : IF (output_unit > 0) THEN
3106 : WRITE (output_unit, FMT="(T5,A,F23.6)") &
3107 1 : "First spin-flip XAS excitation energy (eV): ", donor_state%sf_evals(1)*evolt
3108 : END IF
3109 : END IF ! do_spin_flip
3110 :
3111 56 : IF (xas_tdp_control%do_singlet) THEN
3112 48 : IF (xas_tdp_unit > 0) THEN
3113 :
3114 : ! Printing the general donor state information
3115 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3116 24 : "==================================================================================", &
3117 24 : "XAS TDP singlet excitations (no SOC) for DONOR STATE: ", &
3118 24 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3119 24 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3120 24 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3121 48 : "=================================================================================="
3122 :
3123 : ! Simply dump the excitation energies/ oscillator strength as they come
3124 :
3125 24 : IF (xas_tdp_control%do_quad) THEN
3126 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3127 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3128 0 : DO i = 1, SIZE(donor_state%sg_evals)
3129 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3130 0 : i, donor_state%sg_evals(i)*evolt, donor_state%osc_str(i, 4), &
3131 0 : donor_state%quad_osc_str(i)
3132 : END DO
3133 24 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3134 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3135 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3136 0 : DO i = 1, SIZE(donor_state%sg_evals)
3137 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3138 0 : i, donor_state%sg_evals(i)*evolt, donor_state%osc_str(i, 4), &
3139 0 : donor_state%osc_str(i, 1), donor_state%osc_str(i, 2), donor_state%osc_str(i, 3)
3140 : END DO
3141 : ELSE
3142 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3143 24 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3144 348 : DO i = 1, SIZE(donor_state%sg_evals)
3145 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3146 348 : i, donor_state%sg_evals(i)*evolt, donor_state%osc_str(i, 4)
3147 : END DO
3148 : END IF
3149 :
3150 24 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3151 : END IF !xas_tdp_unit
3152 :
3153 48 : IF (output_unit > 0) THEN
3154 : WRITE (output_unit, FMT="(T5,A,F25.6)") &
3155 24 : "First singlet XAS excitation energy (eV): ", donor_state%sg_evals(1)*evolt
3156 : END IF
3157 : END IF ! do_singlet
3158 :
3159 56 : IF (xas_tdp_control%do_triplet) THEN
3160 2 : IF (xas_tdp_unit > 0) THEN
3161 :
3162 : ! Printing the general donor state information
3163 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3164 1 : "==================================================================================", &
3165 1 : "XAS TDP triplet excitations (no SOC) for DONOR STATE: ", &
3166 1 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3167 1 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3168 1 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3169 2 : "=================================================================================="
3170 :
3171 : ! Simply dump the excitation energies/ oscillator strength as they come
3172 :
3173 1 : IF (xas_tdp_control%do_quad) THEN
3174 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3175 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3176 0 : DO i = 1, SIZE(donor_state%tp_evals)
3177 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3178 0 : i, donor_state%tp_evals(i)*evolt, 0.0_dp, 0.0_dp !spin-forbidden !
3179 : END DO
3180 1 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3181 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3182 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3183 0 : DO i = 1, SIZE(donor_state%tp_evals)
3184 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3185 0 : i, donor_state%tp_evals(i)*evolt, 0.0_dp, 0.0_dp, 0.0_dp, 0.0_dp
3186 : END DO
3187 : ELSE
3188 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3189 1 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3190 13 : DO i = 1, SIZE(donor_state%tp_evals)
3191 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3192 13 : i, donor_state%tp_evals(i)*evolt, 0.0_dp
3193 : END DO
3194 : END IF
3195 :
3196 1 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3197 : END IF !xas_tdp_unit
3198 :
3199 2 : IF (output_unit > 0) THEN
3200 : WRITE (output_unit, FMT="(T5,A,F25.6)") &
3201 1 : "First triplet XAS excitation energy (eV): ", donor_state%tp_evals(1)*evolt
3202 : END IF
3203 : END IF ! do_triplet
3204 :
3205 56 : IF (xas_tdp_control%do_soc .AND. donor_state%state_type == xas_2p_type) THEN
3206 4 : IF (xas_tdp_unit > 0) THEN
3207 :
3208 : ! Printing the general donor state information
3209 : WRITE (xas_tdp_unit, FMT="(A,/,A,A,A/,A,I5,A,I5,A,A,/,A)") &
3210 2 : "==================================================================================", &
3211 2 : "XAS TDP excitations after spin-orbit coupling for DONOR STATE: ", &
3212 2 : xas_tdp_env%state_type_char(donor_state%state_type), ",", &
3213 2 : "from EXCITED ATOM: ", donor_state%at_index, ", of KIND (index/symbol): ", &
3214 2 : donor_state%kind_index, "/", TRIM(donor_state%at_symbol), &
3215 4 : "=================================================================================="
3216 :
3217 : ! Simply dump the excitation energies/ oscillator strength as they come
3218 2 : IF (xas_tdp_control%do_quad) THEN
3219 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3220 0 : " Index Excitation energy (eV) fosc dipole (a.u.) fosc quadrupole (a.u.)"
3221 0 : DO i = 1, SIZE(donor_state%soc_evals)
3222 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F25.6)") &
3223 0 : i, donor_state%soc_evals(i)*evolt, donor_state%soc_osc_str(i, 4), &
3224 0 : donor_state%soc_quad_osc_str(i)
3225 : END DO
3226 2 : ELSE IF (xas_tdp_control%xyz_dip) THEN
3227 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3228 0 : " Index Excitation energy (eV) fosc dipole (a.u.) x-component y-component z-component"
3229 0 : DO i = 1, SIZE(donor_state%soc_evals)
3230 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6,F14.6,F14.6,F14.6)") &
3231 0 : i, donor_state%soc_evals(i)*evolt, donor_state%soc_osc_str(i, 4), &
3232 0 : donor_state%soc_osc_str(i, 1), donor_state%soc_osc_str(i, 2), donor_state%soc_osc_str(i, 3)
3233 : END DO
3234 : ELSE
3235 : WRITE (xas_tdp_unit, FMT="(T3,A)") &
3236 2 : " Index Excitation energy (eV) fosc dipole (a.u.)"
3237 74 : DO i = 1, SIZE(donor_state%soc_evals)
3238 : WRITE (xas_tdp_unit, FMT="(T3,I6,F27.6,F22.6)") &
3239 74 : i, donor_state%soc_evals(i)*evolt, donor_state%soc_osc_str(i, 4)
3240 : END DO
3241 : END IF
3242 :
3243 2 : WRITE (xas_tdp_unit, FMT="(A,/)") " "
3244 : END IF !xas_tdp_unit
3245 :
3246 4 : IF (output_unit > 0) THEN
3247 : WRITE (output_unit, FMT="(T5,A,F29.6)") &
3248 2 : "First SOC XAS excitation energy (eV): ", donor_state%soc_evals(1)*evolt
3249 : END IF
3250 : END IF !do_soc
3251 :
3252 56 : CALL cp_print_key_finished_output(xas_tdp_unit, logger, xas_tdp_section, "PRINT%SPECTRUM")
3253 :
3254 56 : END SUBROUTINE print_xas_tdp_to_file
3255 :
3256 : ! **************************************************************************************************
3257 : !> \brief Prints the donor_state and excitation_type info into a RESTART file for cheap PDOS and/or
3258 : !> CUBE printing without expensive computation
3259 : !> \param ex_type singlet, triplet, etc.
3260 : !> \param donor_state ...
3261 : !> \param xas_tdp_section ...
3262 : !> \param qs_env ...
3263 : ! **************************************************************************************************
3264 64 : SUBROUTINE write_donor_state_restart(ex_type, donor_state, xas_tdp_section, qs_env)
3265 :
3266 : INTEGER, INTENT(IN) :: ex_type
3267 : TYPE(donor_state_type), POINTER :: donor_state
3268 : TYPE(section_vals_type), POINTER :: xas_tdp_section
3269 : TYPE(qs_environment_type), POINTER :: qs_env
3270 :
3271 : CHARACTER(len=*), PARAMETER :: routineN = 'write_donor_state_restart'
3272 :
3273 : CHARACTER(len=default_path_length) :: filename
3274 : CHARACTER(len=default_string_length) :: domo, excite, my_middle
3275 : INTEGER :: ex_atom, handle, ispin, nao, ndo_mo, &
3276 : nex, nspins, output_unit, rst_unit, &
3277 : state_type
3278 60 : INTEGER, DIMENSION(:, :), POINTER :: mo_indices
3279 : LOGICAL :: do_print
3280 60 : REAL(dp), DIMENSION(:), POINTER :: lr_evals
3281 : TYPE(cp_fm_type), POINTER :: lr_coeffs
3282 : TYPE(cp_logger_type), POINTER :: logger
3283 60 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
3284 : TYPE(section_vals_type), POINTER :: print_key
3285 :
3286 60 : NULLIFY (logger, lr_coeffs, lr_evals, print_key, mos)
3287 :
3288 : !Initialization
3289 120 : logger => cp_get_default_logger()
3290 60 : do_print = .FALSE.
3291 60 : IF (BTEST(cp_print_key_should_output(logger%iter_info, xas_tdp_section, &
3292 : "PRINT%RESTART", used_print_key=print_key), cp_p_file)) do_print = .TRUE.
3293 :
3294 58 : IF (.NOT. do_print) RETURN
3295 :
3296 2 : CALL timeset(routineN, handle)
3297 :
3298 2 : output_unit = cp_logger_get_default_io_unit()
3299 :
3300 : !Get general info
3301 2 : SELECT CASE (ex_type)
3302 : CASE (tddfpt_spin_cons)
3303 0 : lr_evals => donor_state%sc_evals
3304 0 : lr_coeffs => donor_state%sc_coeffs
3305 0 : excite = "spincons"
3306 0 : nspins = 2
3307 : CASE (tddfpt_spin_flip)
3308 0 : lr_evals => donor_state%sf_evals
3309 0 : lr_coeffs => donor_state%sf_coeffs
3310 0 : excite = "spinflip"
3311 0 : nspins = 2
3312 : CASE (tddfpt_singlet)
3313 2 : lr_evals => donor_state%sg_evals
3314 2 : lr_coeffs => donor_state%sg_coeffs
3315 2 : excite = "singlet"
3316 2 : nspins = 1
3317 : CASE (tddfpt_triplet)
3318 0 : lr_evals => donor_state%tp_evals
3319 0 : lr_coeffs => donor_state%tp_coeffs
3320 0 : excite = "triplet"
3321 2 : nspins = 1
3322 : END SELECT
3323 :
3324 4 : SELECT CASE (donor_state%state_type)
3325 : CASE (xas_1s_type)
3326 2 : domo = "1s"
3327 : CASE (xas_2s_type)
3328 0 : domo = "2s"
3329 : CASE (xas_2p_type)
3330 2 : domo = "2p"
3331 : END SELECT
3332 :
3333 2 : ndo_mo = donor_state%ndo_mo
3334 2 : nex = SIZE(lr_evals)
3335 2 : CALL cp_fm_get_info(lr_coeffs, nrow_global=nao)
3336 2 : state_type = donor_state%state_type
3337 2 : ex_atom = donor_state%at_index
3338 2 : mo_indices => donor_state%mo_indices
3339 :
3340 : !Opening restart file
3341 2 : rst_unit = -1
3342 2 : my_middle = 'xasat'//TRIM(ADJUSTL(cp_to_string(ex_atom)))//'_'//TRIM(domo)//'_'//TRIM(excite)
3343 : rst_unit = cp_print_key_unit_nr(logger, xas_tdp_section, "PRINT%RESTART", extension=".rst", &
3344 : file_status="REPLACE", file_action="WRITE", &
3345 2 : file_form="UNFORMATTED", middle_name=TRIM(my_middle))
3346 :
3347 : filename = cp_print_key_generate_filename(logger, print_key, middle_name=TRIM(my_middle), &
3348 2 : extension=".rst", my_local=.FALSE.)
3349 :
3350 2 : IF (output_unit > 0) THEN
3351 : WRITE (UNIT=output_unit, FMT="(/,T5,A,/T5,A,A,A)") &
3352 1 : "Linear-response orbitals and excitation energies are written in: ", &
3353 2 : '"', TRIM(filename), '"'
3354 : END IF
3355 :
3356 : !Writing
3357 2 : IF (rst_unit > 0) THEN
3358 1 : WRITE (rst_unit) ex_atom, state_type, ndo_mo, ex_type
3359 1 : WRITE (rst_unit) nao, nex, nspins
3360 1 : WRITE (rst_unit) mo_indices(:, :)
3361 1 : WRITE (rst_unit) lr_evals(:)
3362 : END IF
3363 2 : CALL cp_fm_write_unformatted(lr_coeffs, rst_unit)
3364 :
3365 : !The MOs as well (because the may have been localized)
3366 2 : CALL get_qs_env(qs_env, mos=mos)
3367 4 : DO ispin = 1, nspins
3368 4 : CALL cp_fm_write_unformatted(mos(ispin)%mo_coeff, rst_unit)
3369 : END DO
3370 :
3371 : !closing
3372 2 : CALL cp_print_key_finished_output(rst_unit, logger, xas_tdp_section, "PRINT%RESTART")
3373 :
3374 2 : CALL timestop(handle)
3375 :
3376 60 : END SUBROUTINE write_donor_state_restart
3377 :
3378 : ! **************************************************************************************************
3379 : !> \brief Reads donor_state info from a restart file
3380 : !> \param donor_state the pre-allocated donor_state
3381 : !> \param ex_type the excitations stored in this specific file
3382 : !> \param filename the restart file to read from
3383 : !> \param qs_env ...
3384 : ! **************************************************************************************************
3385 2 : SUBROUTINE read_donor_state_restart(donor_state, ex_type, filename, qs_env)
3386 :
3387 : TYPE(donor_state_type), POINTER :: donor_state
3388 : INTEGER, INTENT(OUT) :: ex_type
3389 : CHARACTER(len=*), INTENT(IN) :: filename
3390 : TYPE(qs_environment_type), POINTER :: qs_env
3391 :
3392 : CHARACTER(len=*), PARAMETER :: routineN = 'read_donor_state_restart'
3393 :
3394 : INTEGER :: handle, ispin, nao, nex, nspins, &
3395 : output_unit, read_params(7), rst_unit
3396 2 : INTEGER, DIMENSION(:, :), POINTER :: mo_indices
3397 : LOGICAL :: file_exists
3398 2 : REAL(dp), DIMENSION(:), POINTER :: lr_evals
3399 : TYPE(cp_blacs_env_type), POINTER :: blacs_env
3400 : TYPE(cp_fm_struct_type), POINTER :: fm_struct
3401 : TYPE(cp_fm_type), POINTER :: lr_coeffs
3402 2 : TYPE(mo_set_type), DIMENSION(:), POINTER :: mos
3403 : TYPE(mp_comm_type) :: group
3404 : TYPE(mp_para_env_type), POINTER :: para_env
3405 :
3406 2 : NULLIFY (lr_evals, lr_coeffs, para_env, fm_struct, blacs_env, mos)
3407 :
3408 2 : CALL timeset(routineN, handle)
3409 :
3410 2 : output_unit = cp_logger_get_default_io_unit()
3411 2 : CPASSERT(ASSOCIATED(donor_state))
3412 2 : CALL get_qs_env(qs_env, para_env=para_env, blacs_env=blacs_env)
3413 2 : group = para_env
3414 :
3415 2 : file_exists = .FALSE.
3416 2 : rst_unit = -1
3417 :
3418 2 : IF (para_env%is_source()) THEN
3419 :
3420 1 : INQUIRE (FILE=filename, EXIST=file_exists)
3421 1 : IF (.NOT. file_exists) CPABORT("Trying to read non-existing XAS_TDP restart file")
3422 :
3423 : CALL open_file(file_name=TRIM(filename), file_action="READ", file_form="UNFORMATTED", &
3424 1 : file_position="REWIND", file_status="OLD", unit_number=rst_unit)
3425 : END IF
3426 :
3427 2 : IF (output_unit > 0) THEN
3428 : WRITE (UNIT=output_unit, FMT="(/,T5,A,/,T5,A,A,A)") &
3429 1 : "Reading linear-response orbitals and excitation energies from file: ", &
3430 2 : '"', filename, '"'
3431 : END IF
3432 :
3433 : !read general params
3434 2 : IF (rst_unit > 0) THEN
3435 1 : READ (rst_unit) read_params(1:4)
3436 1 : READ (rst_unit) read_params(5:7)
3437 : END IF
3438 2 : CALL group%bcast(read_params)
3439 2 : donor_state%at_index = read_params(1)
3440 2 : donor_state%state_type = read_params(2)
3441 2 : donor_state%ndo_mo = read_params(3)
3442 2 : ex_type = read_params(4)
3443 2 : nao = read_params(5)
3444 2 : nex = read_params(6)
3445 2 : nspins = read_params(7)
3446 :
3447 8 : ALLOCATE (mo_indices(donor_state%ndo_mo, nspins))
3448 2 : IF (rst_unit > 0) THEN
3449 1 : READ (rst_unit) mo_indices(1:donor_state%ndo_mo, 1:nspins)
3450 : END IF
3451 10 : CALL group%bcast(mo_indices)
3452 2 : donor_state%mo_indices => mo_indices
3453 :
3454 : !read evals
3455 6 : ALLOCATE (lr_evals(nex))
3456 2 : IF (rst_unit > 0) READ (rst_unit) lr_evals(1:nex)
3457 78 : CALL group%bcast(lr_evals)
3458 :
3459 : !read evecs
3460 : CALL cp_fm_struct_create(fm_struct, context=blacs_env, para_env=para_env, &
3461 2 : nrow_global=nao, ncol_global=nex*donor_state%ndo_mo*nspins)
3462 2 : ALLOCATE (lr_coeffs)
3463 2 : CALL cp_fm_create(lr_coeffs, fm_struct)
3464 2 : CALL cp_fm_read_unformatted(lr_coeffs, rst_unit)
3465 2 : CALL cp_fm_struct_release(fm_struct)
3466 :
3467 : !read MO coeffs and replace in qs_env
3468 2 : CALL get_qs_env(qs_env, mos=mos)
3469 4 : DO ispin = 1, nspins
3470 4 : CALL cp_fm_read_unformatted(mos(ispin)%mo_coeff, rst_unit)
3471 : END DO
3472 :
3473 : !closing file
3474 2 : IF (para_env%is_source()) THEN
3475 1 : CALL close_file(unit_number=rst_unit)
3476 : END IF
3477 :
3478 : !case study on excitation type
3479 2 : SELECT CASE (ex_type)
3480 : CASE (tddfpt_spin_cons)
3481 0 : donor_state%sc_evals => lr_evals
3482 0 : donor_state%sc_coeffs => lr_coeffs
3483 : CASE (tddfpt_spin_flip)
3484 0 : donor_state%sf_evals => lr_evals
3485 0 : donor_state%sf_coeffs => lr_coeffs
3486 : CASE (tddfpt_singlet)
3487 2 : donor_state%sg_evals => lr_evals
3488 2 : donor_state%sg_coeffs => lr_coeffs
3489 : CASE (tddfpt_triplet)
3490 0 : donor_state%tp_evals => lr_evals
3491 2 : donor_state%tp_coeffs => lr_coeffs
3492 : END SELECT
3493 :
3494 2 : CALL timestop(handle)
3495 :
3496 2 : END SUBROUTINE read_donor_state_restart
3497 :
3498 : ! **************************************************************************************************
3499 : !> \brief Checks whether this is a restart calculation and runs it if so
3500 : !> \param rst_filename the file to read for restart
3501 : !> \param xas_tdp_section ...
3502 : !> \param qs_env ...
3503 : ! **************************************************************************************************
3504 4 : SUBROUTINE restart_calculation(rst_filename, xas_tdp_section, qs_env)
3505 :
3506 : CHARACTER(len=*), INTENT(IN) :: rst_filename
3507 : TYPE(section_vals_type), POINTER :: xas_tdp_section
3508 : TYPE(qs_environment_type), POINTER :: qs_env
3509 :
3510 : INTEGER :: ex_type
3511 : TYPE(donor_state_type), POINTER :: donor_state
3512 : TYPE(xas_tdp_env_type), POINTER :: xas_tdp_env
3513 :
3514 2 : NULLIFY (xas_tdp_env, donor_state)
3515 :
3516 : !create a donor_state that we fill with the information we read
3517 2 : ALLOCATE (donor_state)
3518 2 : CALL donor_state_create(donor_state)
3519 2 : CALL read_donor_state_restart(donor_state, ex_type, rst_filename, qs_env)
3520 :
3521 : !create a dummy xas_tdp_env and compute the post XAS_TDP stuff
3522 2 : CALL xas_tdp_env_create(xas_tdp_env)
3523 2 : CALL xas_tdp_post(ex_type, donor_state, xas_tdp_env, xas_tdp_section, qs_env)
3524 :
3525 : !clean-up
3526 2 : CALL xas_tdp_env_release(xas_tdp_env)
3527 2 : CALL free_ds_memory(donor_state)
3528 2 : DEALLOCATE (donor_state%mo_indices)
3529 2 : DEALLOCATE (donor_state)
3530 :
3531 2 : END SUBROUTINE restart_calculation
3532 :
3533 : END MODULE xas_tdp_methods
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