-
Notifications
You must be signed in to change notification settings - Fork 0
/
atom_kind_orbitals.F
1340 lines (1213 loc) · 52.8 KB
/
atom_kind_orbitals.F
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
244
245
246
247
248
249
250
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
293
294
295
296
297
298
299
300
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
331
332
333
334
335
336
337
338
339
340
341
342
343
344
345
346
347
348
349
350
351
352
353
354
355
356
357
358
359
360
361
362
363
364
365
366
367
368
369
370
371
372
373
374
375
376
377
378
379
380
381
382
383
384
385
386
387
388
389
390
391
392
393
394
395
396
397
398
399
400
401
402
403
404
405
406
407
408
409
410
411
412
413
414
415
416
417
418
419
420
421
422
423
424
425
426
427
428
429
430
431
432
433
434
435
436
437
438
439
440
441
442
443
444
445
446
447
448
449
450
451
452
453
454
455
456
457
458
459
460
461
462
463
464
465
466
467
468
469
470
471
472
473
474
475
476
477
478
479
480
481
482
483
484
485
486
487
488
489
490
491
492
493
494
495
496
497
498
499
500
501
502
503
504
505
506
507
508
509
510
511
512
513
514
515
516
517
518
519
520
521
522
523
524
525
526
527
528
529
530
531
532
533
534
535
536
537
538
539
540
541
542
543
544
545
546
547
548
549
550
551
552
553
554
555
556
557
558
559
560
561
562
563
564
565
566
567
568
569
570
571
572
573
574
575
576
577
578
579
580
581
582
583
584
585
586
587
588
589
590
591
592
593
594
595
596
597
598
599
600
601
602
603
604
605
606
607
608
609
610
611
612
613
614
615
616
617
618
619
620
621
622
623
624
625
626
627
628
629
630
631
632
633
634
635
636
637
638
639
640
641
642
643
644
645
646
647
648
649
650
651
652
653
654
655
656
657
658
659
660
661
662
663
664
665
666
667
668
669
670
671
672
673
674
675
676
677
678
679
680
681
682
683
684
685
686
687
688
689
690
691
692
693
694
695
696
697
698
699
700
701
702
703
704
705
706
707
708
709
710
711
712
713
714
715
716
717
718
719
720
721
722
723
724
725
726
727
728
729
730
731
732
733
734
735
736
737
738
739
740
741
742
743
744
745
746
747
748
749
750
751
752
753
754
755
756
757
758
759
760
761
762
763
764
765
766
767
768
769
770
771
772
773
774
775
776
777
778
779
780
781
782
783
784
785
786
787
788
789
790
791
792
793
794
795
796
797
798
799
800
801
802
803
804
805
806
807
808
809
810
811
812
813
814
815
816
817
818
819
820
821
822
823
824
825
826
827
828
829
830
831
832
833
834
835
836
837
838
839
840
841
842
843
844
845
846
847
848
849
850
851
852
853
854
855
856
857
858
859
860
861
862
863
864
865
866
867
868
869
870
871
872
873
874
875
876
877
878
879
880
881
882
883
884
885
886
887
888
889
890
891
892
893
894
895
896
897
898
899
900
901
902
903
904
905
906
907
908
909
910
911
912
913
914
915
916
917
918
919
920
921
922
923
924
925
926
927
928
929
930
931
932
933
934
935
936
937
938
939
940
941
942
943
944
945
946
947
948
949
950
951
952
953
954
955
956
957
958
959
960
961
962
963
964
965
966
967
968
969
970
971
972
973
974
975
976
977
978
979
980
981
982
983
984
985
986
987
988
989
990
991
992
993
994
995
996
997
998
999
1000
!--------------------------------------------------------------------------------------------------!
! CP2K: A general program to perform molecular dynamics simulations !
! Copyright (C) 2000 - 2019 CP2K developers group !
!--------------------------------------------------------------------------------------------------!
! **************************************************************************************************
!> \brief calculate the orbitals for a given atomic kind type
! **************************************************************************************************
MODULE atom_kind_orbitals
USE ai_onecenter, ONLY: sg_erfc
USE atom_electronic_structure, ONLY: calculate_atom
USE atom_fit, ONLY: atom_fit_density
USE atom_operators, ONLY: atom_int_release,&
atom_int_setup,&
atom_ppint_release,&
atom_ppint_setup,&
atom_relint_release,&
atom_relint_setup
USE atom_types, ONLY: &
CGTO_BASIS, Clementi_geobas, GTO_BASIS, atom_basis_type, atom_gthpot_type, atom_integrals, &
atom_orbitals, atom_potential_type, atom_sgppot_type, atom_type, create_atom_orbs, &
create_atom_type, lmat, release_atom_basis, release_atom_potential, release_atom_type, &
set_atom
USE atom_utils, ONLY: atom_density,&
get_maxl_occ,&
get_maxn_occ
USE atomic_kind_types, ONLY: atomic_kind_type,&
get_atomic_kind
USE basis_set_types, ONLY: get_gto_basis_set,&
gto_basis_set_type
USE external_potential_types, ONLY: all_potential_type,&
get_potential,&
gth_potential_type,&
sgp_potential_type
USE input_constants, ONLY: &
barrier_conf, do_analytic, do_dkh0_atom, do_dkh1_atom, do_dkh2_atom, do_dkh3_atom, &
do_gapw_log, do_nonrel_atom, do_numeric, do_rks_atom, do_sczoramp_atom, do_uks_atom, &
do_zoramp_atom, gth_pseudo, no_pseudo, poly_conf, rel_dkh, rel_none, rel_sczora_mp, &
rel_zora, rel_zora_full, rel_zora_mp, sgp_pseudo
USE input_section_types, ONLY: section_vals_type
USE kinds, ONLY: dp
USE mathconstants, ONLY: dfac,&
pi
USE periodic_table, ONLY: ptable
USE physcon, ONLY: bohr
USE qs_grid_atom, ONLY: allocate_grid_atom,&
create_grid_atom,&
grid_atom_type
USE qs_kind_types, ONLY: get_qs_kind,&
init_atom_electronic_state,&
qs_kind_type,&
set_pseudo_state
USE rel_control_types, ONLY: rel_control_type
#include "./base/base_uses.f90"
IMPLICIT NONE
PRIVATE
CHARACTER(len=*), PARAMETER, PRIVATE :: moduleN = 'atom_kind_orbitals'
INTEGER, PARAMETER :: nua = 40, nup = 20
REAL(KIND=dp), DIMENSION(nua), PARAMETER :: ugbs = (/0.007299_dp, 0.013705_dp, 0.025733_dp, &
0.048316_dp, 0.090718_dp, 0.170333_dp, 0.319819_dp, 0.600496_dp, 1.127497_dp, 2.117000_dp, &
3.974902_dp, 7.463317_dp, 14.013204_dp, 26.311339_dp, 49.402449_dp, 92.758561_dp, &
174.164456_dp, 327.013024_dp, 614.003114_dp, 1152.858743_dp, 2164.619772_dp, &
4064.312984_dp, 7631.197056_dp, 14328.416324_dp, 26903.186074_dp, 50513.706789_dp, &
94845.070265_dp, 178082.107320_dp, 334368.848683_dp, 627814.487663_dp, 1178791.123851_dp, &
2213310.684886_dp, 4155735.557141_dp, 7802853.046713_dp, 14650719.428954_dp, &
27508345.793637_dp, 51649961.080194_dp, 96978513.342764_dp, 182087882.613702_dp, &
341890134.751331_dp/)
PUBLIC :: calculate_atomic_orbitals, calculate_atomic_density, &
calculate_atomic_relkin, gth_potential_conversion
! **************************************************************************************************
CONTAINS
! **************************************************************************************************
!> \brief ...
!> \param atomic_kind ...
!> \param qs_kind ...
!> \param agrid ...
!> \param iunit ...
!> \param pmat ...
!> \param fmat ...
!> \param density ...
!> \param wavefunction ...
!> \param wfninfo ...
!> \param confine ...
!> \param xc_section ...
!> \param nocc ...
! **************************************************************************************************
SUBROUTINE calculate_atomic_orbitals(atomic_kind, qs_kind, agrid, iunit, pmat, fmat, &
density, wavefunction, wfninfo, confine, xc_section, nocc)
TYPE(atomic_kind_type), INTENT(IN) :: atomic_kind
TYPE(qs_kind_type), INTENT(IN) :: qs_kind
TYPE(grid_atom_type), OPTIONAL :: agrid
INTEGER, INTENT(IN), OPTIONAL :: iunit
REAL(KIND=dp), DIMENSION(:, :, :), OPTIONAL, &
POINTER :: pmat, fmat
REAL(KIND=dp), DIMENSION(:), OPTIONAL, POINTER :: density
REAL(KIND=dp), DIMENSION(:, :), OPTIONAL, POINTER :: wavefunction, wfninfo
LOGICAL, INTENT(IN), OPTIONAL :: confine
TYPE(section_vals_type), OPTIONAL, POINTER :: xc_section
INTEGER, DIMENSION(:), OPTIONAL :: nocc
CHARACTER(len=*), PARAMETER :: routineN = 'calculate_atomic_orbitals', &
routineP = moduleN//':'//routineN
INTEGER :: i, ii, ipgf, j, k, k1, k2, l, ll, m, mb, &
mo, ngp, nj, nr, ns, nset, nsgf, nu, &
quadtype, z
INTEGER, DIMENSION(0:lmat, 10) :: ncalc, ncore, nelem
INTEGER, DIMENSION(0:lmat, 100) :: set_index, shell_index
INTEGER, DIMENSION(:), POINTER :: lmax, lmin, npgf, nshell
INTEGER, DIMENSION(:, :), POINTER :: first_sgf, last_sgf, ls
LOGICAL :: has_basis, uks
REAL(KIND=dp) :: al, ear, ok, rk, scal, zeff
REAL(KIND=dp), DIMENSION(0:lmat, 10, 2) :: edelta
REAL(KIND=dp), DIMENSION(:, :), POINTER :: zet
REAL(KIND=dp), DIMENSION(:, :, :), POINTER :: gcc
TYPE(all_potential_type), POINTER :: all_potential
TYPE(atom_basis_type), POINTER :: basis
TYPE(atom_integrals), POINTER :: integrals
TYPE(atom_orbitals), POINTER :: orbitals
TYPE(atom_potential_type), POINTER :: potential
TYPE(atom_type), POINTER :: atom
TYPE(grid_atom_type), POINTER :: grid
TYPE(gth_potential_type), POINTER :: gth_potential
TYPE(gto_basis_set_type), POINTER :: orb_basis_set
TYPE(sgp_potential_type), POINTER :: sgp_potential
NULLIFY (atom)
CALL create_atom_type(atom)
IF (PRESENT(xc_section)) THEN
atom%xc_section => xc_section
ELSE
NULLIFY (atom%xc_section)
END IF
CALL get_atomic_kind(atomic_kind, z=z)
NULLIFY (all_potential, gth_potential, sgp_potential, orb_basis_set)
CALL get_qs_kind(qs_kind, zeff=zeff, &
basis_set=orb_basis_set, &
all_potential=all_potential, &
gth_potential=gth_potential, &
sgp_potential=sgp_potential)
IF (ASSOCIATED(orb_basis_set)) THEN
has_basis = .TRUE.
ELSE
has_basis = .FALSE.
END IF
atom%z = z
CALL set_atom(atom, &
pp_calc=(ASSOCIATED(gth_potential) .OR. ASSOCIATED(sgp_potential)), &
do_zmp=.FALSE., &
doread=.FALSE., &
read_vxc=.FALSE., &
relativistic=do_nonrel_atom, &
coulomb_integral_type=do_numeric, &
exchange_integral_type=do_numeric)
ALLOCATE (potential, basis, integrals)
IF (PRESENT(confine)) THEN
potential%confinement = confine
ELSE
IF (ASSOCIATED(gth_potential) .OR. ASSOCIATED(sgp_potential)) THEN
potential%confinement = .TRUE.
ELSE
potential%confinement = .FALSE.
END IF
END IF
potential%conf_type = poly_conf
potential%acon = 0.1_dp
potential%rcon = 2.0_dp*ptable(z)%vdw_radius*bohr
potential%scon = 2.0_dp
IF (ASSOCIATED(gth_potential)) THEN
potential%ppot_type = gth_pseudo
CALL get_potential(gth_potential, zeff=zeff)
CALL gth_potential_conversion(gth_potential, potential%gth_pot)
CALL set_atom(atom, zcore=NINT(zeff), potential=potential)
ELSE IF (ASSOCIATED(sgp_potential)) THEN
potential%ppot_type = sgp_pseudo
CALL sgp_potential_conversion(sgp_potential, potential%sgp_pot)
potential%sgp_pot%symbol = ptable(z)%symbol
CALL get_potential(sgp_potential, zeff=zeff)
CALL set_atom(atom, zcore=NINT(zeff), potential=potential)
ELSE
potential%ppot_type = no_pseudo
CALL set_atom(atom, zcore=z, potential=potential)
END IF
NULLIFY (grid)
IF (PRESENT(agrid)) THEN
ngp = agrid%nr
quadtype = agrid%quadrature
ELSE
ngp = 400
quadtype = do_gapw_log
END IF
CALL allocate_grid_atom(grid)
CALL create_grid_atom(grid, ngp, 1, 1, 0, quadtype)
grid%nr = ngp
basis%grid => grid
NULLIFY (basis%am, basis%cm, basis%as, basis%ns, basis%bf, basis%dbf, basis%ddbf)
IF (has_basis) THEN
! fill in the basis data structures
basis%basis_type = CGTO_BASIS
basis%eps_eig = 1.e-12_dp
CALL get_gto_basis_set(orb_basis_set, &
nset=nset, nshell=nshell, npgf=npgf, lmin=lmin, lmax=lmax, &
l=ls, nsgf=nsgf, zet=zet, gcc=gcc, &
first_sgf=first_sgf, last_sgf=last_sgf)
set_index = 0
shell_index = 0
basis%nprim = 0
basis%nbas = 0
DO i = 1, nset
DO j = lmin(i), MIN(lmax(i), lmat)
basis%nprim(j) = basis%nprim(j)+npgf(i)
END DO
DO j = 1, nshell(i)
l = ls(j, i)
IF (l <= lmat) THEN
basis%nbas(l) = basis%nbas(l)+1
k = basis%nbas(l)
CPASSERT(k <= 100)
set_index(l, k) = i
shell_index(l, k) = j
END IF
END DO
END DO
nj = MAXVAL(basis%nprim)
ns = MAXVAL(basis%nbas)
ALLOCATE (basis%am(nj, 0:lmat))
basis%am = 0._dp
ALLOCATE (basis%cm(nj, ns, 0:lmat))
basis%cm = 0._dp
DO j = 0, lmat
nj = 0
ns = 0
DO i = 1, nset
IF (j >= lmin(i) .AND. j <= lmax(i)) THEN
DO ipgf = 1, npgf(i)
basis%am(nj+ipgf, j) = zet(ipgf, i)
END DO
DO ii = 1, nshell(i)
IF (ls(ii, i) == j) THEN
ns = ns+1
DO ipgf = 1, npgf(i)
basis%cm(nj+ipgf, ns, j) = gcc(ipgf, ii, i)
END DO
END IF
END DO
nj = nj+npgf(i)
END IF
END DO
END DO
ELSE
! use default basis
IF (ASSOCIATED(gth_potential) .OR. ASSOCIATED(sgp_potential)) THEN
nu = nup
ELSE
nu = nua
END IF
basis%geometrical = .FALSE.
basis%aval = 0._dp
basis%cval = 0._dp
basis%start = 0
basis%eps_eig = 1.e-12_dp
basis%basis_type = GTO_BASIS
basis%nbas = nu
basis%nprim = nu
ALLOCATE (basis%am(nu, 0:lmat))
DO i = 0, lmat
basis%am(1:nu, i) = ugbs(1:nu)
END DO
END IF
! initialize basis function on a radial grid
nr = basis%grid%nr
m = MAXVAL(basis%nbas)
ALLOCATE (basis%bf(nr, m, 0:lmat))
ALLOCATE (basis%dbf(nr, m, 0:lmat))
ALLOCATE (basis%ddbf(nr, m, 0:lmat))
basis%bf = 0._dp
basis%dbf = 0._dp
basis%ddbf = 0._dp
DO l = 0, lmat
DO i = 1, basis%nprim(l)
al = basis%am(i, l)
IF (basis%basis_type == GTO_BASIS) THEN
DO k = 1, nr
rk = basis%grid%rad(k)
ear = EXP(-al*basis%grid%rad(k)**2)
basis%bf(k, i, l) = rk**l*ear
basis%dbf(k, i, l) = (REAL(l, dp)*rk**(l-1)-2._dp*al*rk**(l+1))*ear
basis%ddbf(k, i, l) = (REAL(l*(l-1), dp)*rk**(l-2)- &
2._dp*al*REAL(2*l+1, dp)*rk**(l)+4._dp*al*rk**(l+2))*ear
END DO
ELSEIF (basis%basis_type == CGTO_BASIS) THEN
DO k = 1, nr
rk = basis%grid%rad(k)
ear = EXP(-al*basis%grid%rad(k)**2)
DO j = 1, basis%nbas(l)
basis%bf(k, j, l) = basis%bf(k, j, l)+rk**l*ear*basis%cm(i, j, l)
basis%dbf(k, j, l) = basis%dbf(k, j, l) &
+(REAL(l, dp)*rk**(l-1)-2._dp*al*rk**(l+1))*ear*basis%cm(i, j, l)
basis%ddbf(k, j, l) = basis%ddbf(k, j, l)+ &
(REAL(l*(l-1), dp)*rk**(l-2)-2._dp*al*REAL(2*l+1, dp)*rk**(l)+ &
4._dp*al*rk**(l+2))*ear*basis%cm(i, j, l)
END DO
END DO
ELSE
CPABORT('Atom basis type?')
END IF
END DO
END DO
CALL set_atom(atom, basis=basis)
! optimization defaults
atom%optimization%damping = 0.2_dp
atom%optimization%eps_scf = 1.e-6_dp
atom%optimization%eps_diis = 100._dp
atom%optimization%max_iter = 50
atom%optimization%n_diis = 5
! set up the electronic state
CALL init_atom_electronic_state(atomic_kind=atomic_kind, &
qs_kind=qs_kind, &
ncalc=ncalc, &
ncore=ncore, &
nelem=nelem, &
edelta=edelta)
! restricted or unrestricted?
IF (SUM(ABS(edelta)) > 0.0_dp) THEN
uks = .TRUE.
CALL set_atom(atom, method_type=do_uks_atom)
ELSE
uks = .FALSE.
CALL set_atom(atom, method_type=do_rks_atom)
END IF
ALLOCATE (atom%state)
atom%state%core = 0._dp
atom%state%core(0:lmat, 1:7) = REAL(ncore(0:lmat, 1:7), dp)
atom%state%occ = 0._dp
IF (uks) THEN
atom%state%occ(0:lmat, 1:7) = REAL(ncalc(0:lmat, 1:7), dp)+ &
edelta(0:lmat, 1:7, 1)+edelta(0:lmat, 1:7, 2)
ELSE
atom%state%occ(0:lmat, 1:7) = REAL(ncalc(0:lmat, 1:7), dp)
END IF
atom%state%occupation = 0._dp
DO l = 0, lmat
k = 0
DO i = 1, 7
IF (ncalc(l, i) > 0) THEN
k = k+1
IF (uks) THEN
atom%state%occupation(l, k) = REAL(ncalc(l, i), dp)+ &
edelta(l, i, 1)+edelta(l, i, 2)
atom%state%occa(l, k) = 0.5_dp*REAL(ncalc(l, i), dp)+edelta(l, i, 1)
atom%state%occb(l, k) = 0.5_dp*REAL(ncalc(l, i), dp)+edelta(l, i, 2)
ELSE
atom%state%occupation(l, k) = REAL(ncalc(l, i), dp)
END IF
END IF
END DO
ok = REAL(2*l+1, KIND=dp)
IF (uks) THEN
DO i = 1, 7
atom%state%occ(l, i) = MIN(atom%state%occ(l, i), 2.0_dp*ok)
atom%state%occa(l, i) = MIN(atom%state%occa(l, i), ok)
atom%state%occb(l, i) = MIN(atom%state%occb(l, i), ok)
atom%state%occupation(l, i) = atom%state%occa(l, i)+atom%state%occb(l, i)
END DO
ELSE
DO i = 1, 7
atom%state%occ(l, i) = MIN(atom%state%occ(l, i), 2.0_dp*ok)
atom%state%occupation(l, i) = MIN(atom%state%occupation(l, i), 2.0_dp*ok)
END DO
END IF
END DO
IF (uks) THEN
atom%state%multiplicity = NINT(ABS(SUM(atom%state%occa-atom%state%occb))+1)
ELSE
atom%state%multiplicity = -1
END IF
atom%state%maxl_occ = get_maxl_occ(atom%state%occupation)
atom%state%maxn_occ = get_maxn_occ(atom%state%occupation)
atom%state%maxl_calc = atom%state%maxl_occ
atom%state%maxn_calc = atom%state%maxn_occ
! total number of occupied orbitals
IF (PRESENT(nocc)) THEN
nocc = 0
DO l = 0, lmat
DO k = 1, 7
IF (uks) THEN
IF (atom%state%occa(l, k) > 0.0_dp) THEN
nocc(1) = nocc(1)+2*l+1
END IF
IF (atom%state%occb(l, k) > 0.0_dp) THEN
nocc(2) = nocc(2)+2*l+1
END IF
ELSE
IF (atom%state%occupation(l, k) > 0.0_dp) THEN
nocc(1) = nocc(1)+2*l+1
nocc(2) = nocc(2)+2*l+1
END IF
END IF
END DO
END DO
END IF
! calculate integrals
! general integrals
CALL atom_int_setup(integrals, basis, potential=atom%potential, &
eri_coulomb=(atom%coulomb_integral_type == do_analytic), &
eri_exchange=(atom%exchange_integral_type == do_analytic))
! potential
CALL atom_ppint_setup(integrals, basis, potential=atom%potential)
! relativistic correction terms
NULLIFY (integrals%tzora, integrals%hdkh)
CALL atom_relint_setup(integrals, basis, atom%relativistic, zcore=REAL(atom%zcore, dp))
CALL set_atom(atom, integrals=integrals)
NULLIFY (orbitals)
mo = MAXVAL(atom%state%maxn_calc)
mb = MAXVAL(atom%basis%nbas)
CALL create_atom_orbs(orbitals, mb, mo)
CALL set_atom(atom, orbitals=orbitals)
IF (PRESENT(iunit)) THEN
CALL calculate_atom(atom, iunit)
ELSE
CALL calculate_atom(atom, -1)
END IF
IF (PRESENT(pmat)) THEN
! recover density matrix in CP2K/GPW order and normalization
IF (ASSOCIATED(pmat)) THEN
DEALLOCATE (pmat)
END IF
ALLOCATE (pmat(nsgf, nsgf, 2))
pmat = 0._dp
DO l = 0, lmat
ll = 2*l
DO k1 = 1, atom%basis%nbas(l)
DO k2 = 1, atom%basis%nbas(l)
scal = SQRT(atom%integrals%ovlp(k1, k1, l)*atom%integrals%ovlp(k2, k2, l))/REAL(2*l+1, KIND=dp)
i = first_sgf(shell_index(l, k1), set_index(l, k1))
j = first_sgf(shell_index(l, k2), set_index(l, k2))
IF (uks) THEN
DO m = 0, ll
pmat(i+m, j+m, 1) = atom%orbitals%pmata(k1, k2, l)*scal
pmat(i+m, j+m, 2) = atom%orbitals%pmatb(k1, k2, l)*scal
END DO
ELSE
DO m = 0, ll
pmat(i+m, j+m, 1) = atom%orbitals%pmat(k1, k2, l)*scal
END DO
END IF
END DO
END DO
ENDDO
IF (uks) THEN
pmat(:, :, 1) = pmat(:, :, 1)+pmat(:, :, 2)
pmat(:, :, 2) = pmat(:, :, 1)-2.0_dp*pmat(:, :, 2)
END IF
END IF
IF (PRESENT(fmat)) THEN
! recover fock matrix in CP2K/GPW order.
! Caution: Normalization is not take care of, so it's probably weird.
IF (uks) CPABORT("calculate_atomic_orbitals: only RKS is implemented")
IF (ASSOCIATED(fmat)) CPABORT("fmat already associated")
IF (.NOT. ASSOCIATED(atom%fmat)) CPABORT("atom%fmat not associated")
ALLOCATE (fmat(nsgf, nsgf, 1))
fmat = 0.0_dp
DO l = 0, lmat
ll = 2*l
DO k1 = 1, atom%basis%nbas(l)
DO k2 = 1, atom%basis%nbas(l)
scal = SQRT(atom%integrals%ovlp(k1, k1, l)*atom%integrals%ovlp(k2, k2, l))
i = first_sgf(shell_index(l, k1), set_index(l, k1))
j = first_sgf(shell_index(l, k2), set_index(l, k2))
DO m = 0, ll
fmat(i+m, j+m, 1) = atom%fmat%op(k1, k2, l)/scal
END DO
END DO
END DO
ENDDO
END IF
IF (PRESENT(density)) THEN
IF (ASSOCIATED(density)) DEALLOCATE (density)
ALLOCATE (density(nr))
CALL atom_density(density, atom%orbitals%pmat, atom%basis, atom%state%maxl_occ)
END IF
IF (PRESENT(wavefunction)) THEN
CPASSERT(PRESENT(wfninfo))
IF (ASSOCIATED(wavefunction)) DEALLOCATE (wavefunction)
IF (ASSOCIATED(wfninfo)) DEALLOCATE (wfninfo)
mo = SUM(atom%state%maxn_occ)
ALLOCATE (wavefunction(nr, mo), wfninfo(2, mo))
wavefunction = 0.0_dp
ii = 0
DO l = 0, lmat
DO i = 1, atom%state%maxn_occ(l)
IF (atom%state%occupation(l, i) > 0.0_dp) THEN
ii = ii+1
wfninfo(1, ii) = atom%state%occupation(l, i)
wfninfo(2, ii) = REAL(l, dp)
DO j = 1, atom%basis%nbas(l)
wavefunction(:, ii) = wavefunction(:, ii)+ &
atom%orbitals%wfn(j, i, l)*basis%bf(:, j, l)
END DO
END IF
END DO
END DO
CPASSERT(mo == ii)
END IF
! clean up
CALL atom_int_release(integrals)
CALL atom_ppint_release(integrals)
CALL atom_relint_release(integrals)
CALL release_atom_basis(basis)
CALL release_atom_potential(potential)
CALL release_atom_type(atom)
DEALLOCATE (potential, basis, integrals)
END SUBROUTINE calculate_atomic_orbitals
! **************************************************************************************************
!> \brief ...
!> \param density ...
!> \param atomic_kind ...
!> \param qs_kind ...
!> \param ngto ...
!> \param iunit ...
!> \param allelectron ...
!> \param confine ...
! **************************************************************************************************
SUBROUTINE calculate_atomic_density(density, atomic_kind, qs_kind, ngto, iunit, allelectron, confine)
REAL(KIND=dp), DIMENSION(:, :), INTENT(INOUT) :: density
TYPE(atomic_kind_type), POINTER :: atomic_kind
TYPE(qs_kind_type), POINTER :: qs_kind
INTEGER, INTENT(IN) :: ngto
INTEGER, INTENT(IN), OPTIONAL :: iunit
LOGICAL, INTENT(IN), OPTIONAL :: allelectron, confine
CHARACTER(len=*), PARAMETER :: routineN = 'calculate_atomic_density', &
routineP = moduleN//':'//routineN
INTEGER, PARAMETER :: num_gto = 40
INTEGER :: i, ii, k, l, ll, m, mb, mo, ngp, nn, nr, &
quadtype, relativistic, z
INTEGER, DIMENSION(0:lmat) :: starti
INTEGER, DIMENSION(0:lmat, 10) :: ncalc, ncore, nelem
INTEGER, DIMENSION(:), POINTER :: econf
REAL(KIND=dp) :: al, aval, cc, cval, ear, rk, xx, zeff
REAL(KIND=dp), DIMENSION(num_gto+2) :: results
TYPE(all_potential_type), POINTER :: all_potential
TYPE(atom_basis_type), POINTER :: basis
TYPE(atom_integrals), POINTER :: integrals
TYPE(atom_orbitals), POINTER :: orbitals
TYPE(atom_potential_type), POINTER :: potential
TYPE(atom_type), POINTER :: atom
TYPE(grid_atom_type), POINTER :: grid
TYPE(gth_potential_type), POINTER :: gth_potential
TYPE(sgp_potential_type), POINTER :: sgp_potential
NULLIFY (atom)
CALL create_atom_type(atom)
CALL get_atomic_kind(atomic_kind, z=z)
NULLIFY (all_potential, gth_potential)
CALL get_qs_kind(qs_kind, zeff=zeff, &
all_potential=all_potential, &
gth_potential=gth_potential, &
sgp_potential=sgp_potential)
IF (PRESENT(allelectron)) THEN
IF (allelectron) THEN
NULLIFY (gth_potential)
zeff = z
END IF
END IF
CPASSERT(ngto <= num_gto)
IF (ASSOCIATED(gth_potential) .OR. ASSOCIATED(sgp_potential)) THEN
! PP calculation are non-relativistic
relativistic = do_nonrel_atom
ELSE
! AE calculations use DKH2
relativistic = do_dkh2_atom
END IF
atom%z = z
CALL set_atom(atom, &
pp_calc=(ASSOCIATED(gth_potential) .OR. ASSOCIATED(sgp_potential)), &
method_type=do_rks_atom, &
relativistic=relativistic, &
coulomb_integral_type=do_numeric, &
exchange_integral_type=do_numeric)
ALLOCATE (potential, basis, integrals)
IF (PRESENT(confine)) THEN
potential%confinement = confine
ELSE
IF (ASSOCIATED(gth_potential) .OR. ASSOCIATED(sgp_potential)) THEN
potential%confinement = .TRUE.
ELSE
potential%confinement = .FALSE.
END IF
END IF
potential%conf_type = barrier_conf
potential%acon = 200._dp
potential%rcon = 4.0_dp
potential%scon = 8.0_dp
IF (ASSOCIATED(gth_potential)) THEN
potential%ppot_type = gth_pseudo
CALL get_potential(gth_potential, zeff=zeff)
CALL gth_potential_conversion(gth_potential, potential%gth_pot)
CALL set_atom(atom, zcore=NINT(zeff), potential=potential)
ELSE IF (ASSOCIATED(sgp_potential)) THEN
potential%ppot_type = sgp_pseudo
CALL sgp_potential_conversion(sgp_potential, potential%sgp_pot)
potential%sgp_pot%symbol = ptable(z)%symbol
CALL get_potential(sgp_potential, zeff=zeff)
CALL set_atom(atom, zcore=NINT(zeff), potential=potential)
ELSE
potential%ppot_type = no_pseudo
CALL set_atom(atom, zcore=z, potential=potential)
END IF
! atomic grid
NULLIFY (grid)
ngp = 400
quadtype = do_gapw_log
CALL allocate_grid_atom(grid)
CALL create_grid_atom(grid, ngp, 1, 1, 0, quadtype)
grid%nr = ngp
basis%grid => grid
NULLIFY (basis%am, basis%cm, basis%as, basis%ns, basis%bf, basis%dbf, basis%ddbf)
! fill in the basis data structures
basis%eps_eig = 1.e-12_dp
basis%basis_type = GTO_BASIS
CALL Clementi_geobas(z, cval, aval, basis%nbas, starti)
basis%nprim = basis%nbas
m = MAXVAL(basis%nbas)
ALLOCATE (basis%am(m, 0:lmat))
basis%am = 0._dp
DO l = 0, lmat
DO i = 1, basis%nbas(l)
ll = i-1+starti(l)
basis%am(i, l) = aval*cval**(ll)
END DO
END DO
basis%geometrical = .TRUE.
basis%aval = aval
basis%cval = cval
basis%start = starti
! initialize basis function on a radial grid
nr = basis%grid%nr
m = MAXVAL(basis%nbas)
ALLOCATE (basis%bf(nr, m, 0:lmat))
ALLOCATE (basis%dbf(nr, m, 0:lmat))
ALLOCATE (basis%ddbf(nr, m, 0:lmat))
basis%bf = 0._dp
basis%dbf = 0._dp
basis%ddbf = 0._dp
DO l = 0, lmat
DO i = 1, basis%nbas(l)
al = basis%am(i, l)
DO k = 1, nr
rk = basis%grid%rad(k)
ear = EXP(-al*basis%grid%rad(k)**2)
basis%bf(k, i, l) = rk**l*ear
basis%dbf(k, i, l) = (REAL(l, dp)*rk**(l-1)-2._dp*al*rk**(l+1))*ear
basis%ddbf(k, i, l) = (REAL(l*(l-1), dp)*rk**(l-2)- &
2._dp*al*REAL(2*l+1, dp)*rk**(l)+4._dp*al*rk**(l+2))*ear
END DO
END DO
END DO
CALL set_atom(atom, basis=basis)
! optimization defaults
atom%optimization%damping = 0.2_dp
atom%optimization%eps_scf = 1.e-6_dp
atom%optimization%eps_diis = 100._dp
atom%optimization%max_iter = 50
atom%optimization%n_diis = 5
nelem = 0
ncore = 0
ncalc = 0
IF (ASSOCIATED(gth_potential)) THEN
CALL get_potential(gth_potential, elec_conf=econf)
CALL set_pseudo_state(econf, z, ncalc, ncore, nelem)
ELSE IF (ASSOCIATED(sgp_potential)) THEN
CALL get_potential(sgp_potential, elec_conf=econf)
CALL set_pseudo_state(econf, z, ncalc, ncore, nelem)
ELSE
DO l = 0, MIN(lmat, UBOUND(ptable(z)%e_conv, 1))
ll = 2*(2*l+1)
nn = ptable(z)%e_conv(l)
ii = 0
DO
ii = ii+1
IF (nn <= ll) THEN
nelem(l, ii) = nn
EXIT
ELSE
nelem(l, ii) = ll
nn = nn-ll
END IF
END DO
END DO
ncalc = nelem-ncore
END IF
IF (qs_kind%ghost .OR. qs_kind%floating) THEN
nelem = 0
ncore = 0
ncalc = 0
END IF
ALLOCATE (atom%state)
atom%state%core = 0._dp
atom%state%core(0:lmat, 1:7) = REAL(ncore(0:lmat, 1:7), dp)
atom%state%occ = 0._dp
atom%state%occ(0:lmat, 1:7) = REAL(ncalc(0:lmat, 1:7), dp)
atom%state%occupation = 0._dp
atom%state%multiplicity = -1
DO l = 0, lmat
k = 0
DO i = 1, 7
IF (ncalc(l, i) > 0) THEN
k = k+1
atom%state%occupation(l, k) = REAL(ncalc(l, i), dp)
END IF
END DO
END DO
atom%state%maxl_occ = get_maxl_occ(atom%state%occupation)
atom%state%maxn_occ = get_maxn_occ(atom%state%occupation)
atom%state%maxl_calc = atom%state%maxl_occ
atom%state%maxn_calc = atom%state%maxn_occ
! calculate integrals
! general integrals
CALL atom_int_setup(integrals, basis, potential=atom%potential, &
eri_coulomb=(atom%coulomb_integral_type == do_analytic), &
eri_exchange=(atom%exchange_integral_type == do_analytic))
! potential
CALL atom_ppint_setup(integrals, basis, potential=atom%potential)
! relativistic correction terms
NULLIFY (integrals%tzora, integrals%hdkh)
CALL atom_relint_setup(integrals, basis, atom%relativistic, zcore=REAL(atom%zcore, dp))
CALL set_atom(atom, integrals=integrals)
NULLIFY (orbitals)
mo = MAXVAL(atom%state%maxn_calc)
mb = MAXVAL(atom%basis%nbas)
CALL create_atom_orbs(orbitals, mb, mo)
CALL set_atom(atom, orbitals=orbitals)
IF (PRESENT(iunit)) THEN
CALL calculate_atom(atom, iunit)
CALL atom_fit_density(atom, ngto, 0, iunit, results=results)
ELSE
CALL calculate_atom(atom, -1)
CALL atom_fit_density(atom, ngto, 0, -1, results=results)
END IF
xx = results(1)
cc = results(2)
DO i = 1, ngto
density(i, 1) = xx*cc**i
density(i, 2) = results(2+i)
END DO
! clean up
CALL atom_int_release(integrals)
CALL atom_ppint_release(integrals)
CALL atom_relint_release(integrals)
CALL release_atom_basis(basis)
CALL release_atom_potential(potential)
CALL release_atom_type(atom)
DEALLOCATE (potential, basis, integrals)
END SUBROUTINE calculate_atomic_density
! **************************************************************************************************
!> \brief ...
!> \param atomic_kind ...
!> \param qs_kind ...
!> \param rel_control ...
!> \param rtmat ...
! **************************************************************************************************
SUBROUTINE calculate_atomic_relkin(atomic_kind, qs_kind, rel_control, rtmat)
TYPE(atomic_kind_type), INTENT(IN) :: atomic_kind
TYPE(qs_kind_type), INTENT(IN) :: qs_kind
TYPE(rel_control_type), POINTER :: rel_control
REAL(KIND=dp), DIMENSION(:, :), POINTER :: rtmat
CHARACTER(len=*), PARAMETER :: routineN = 'calculate_atomic_relkin', &
routineP = moduleN//':'//routineN
INTEGER :: i, ii, ipgf, j, k, k1, k2, l, ll, m, n, &
ngp, nj, nn, nr, ns, nset, nsgf, &
quadtype, relativistic, z
INTEGER, DIMENSION(0:lmat, 10) :: ncalc, ncore, nelem
INTEGER, DIMENSION(0:lmat, 100) :: set_index, shell_index
INTEGER, DIMENSION(:), POINTER :: lmax, lmin, npgf, nshell
INTEGER, DIMENSION(:, :), POINTER :: first_sgf, last_sgf, ls
REAL(KIND=dp) :: al, alpha, ear, prefac, rk, zeff
REAL(KIND=dp), ALLOCATABLE, DIMENSION(:, :) :: omat
REAL(KIND=dp), DIMENSION(:, :), POINTER :: zet
REAL(KIND=dp), DIMENSION(:, :, :), POINTER :: gcc
TYPE(all_potential_type), POINTER :: all_potential
TYPE(atom_basis_type), POINTER :: basis
TYPE(atom_integrals), POINTER :: integrals
TYPE(atom_potential_type), POINTER :: potential
TYPE(atom_type), POINTER :: atom
TYPE(grid_atom_type), POINTER :: grid
TYPE(gto_basis_set_type), POINTER :: orb_basis_set
IF (rel_control%rel_method == rel_none) RETURN
NULLIFY (all_potential, orb_basis_set)
CALL get_qs_kind(qs_kind, basis_set=orb_basis_set, all_potential=all_potential)
CPASSERT(ASSOCIATED(orb_basis_set))
IF (ASSOCIATED(all_potential)) THEN
! only all electron atoms will get the relativistic correction
CALL get_atomic_kind(atomic_kind, z=z)
CALL get_qs_kind(qs_kind, zeff=zeff)
NULLIFY (atom)
CALL create_atom_type(atom)
NULLIFY (atom%xc_section)
NULLIFY (atom%orbitals)
atom%z = z
alpha = SQRT(all_potential%alpha_core_charge)
! set the method flag
SELECT CASE (rel_control%rel_method)
CASE DEFAULT
CPABORT("")
CASE (rel_dkh)
SELECT CASE (rel_control%rel_DKH_order)
CASE DEFAULT
CPABORT("")
CASE (0)
relativistic = do_dkh0_atom
CASE (1)
relativistic = do_dkh1_atom
CASE (2)
relativistic = do_dkh2_atom
CASE (3)
relativistic = do_dkh3_atom
END SELECT
CASE (rel_zora)
SELECT CASE (rel_control%rel_zora_type)
CASE DEFAULT
CPABORT("")
CASE (rel_zora_full)
CPABORT("")
CASE (rel_zora_mp)
relativistic = do_zoramp_atom
CASE (rel_sczora_mp)
relativistic = do_sczoramp_atom
END SELECT
END SELECT
CALL set_atom(atom, &
pp_calc=.FALSE., &
method_type=do_rks_atom, &
relativistic=relativistic, &
coulomb_integral_type=do_numeric, &
exchange_integral_type=do_numeric)
ALLOCATE (potential, basis, integrals)
potential%ppot_type = no_pseudo
CALL set_atom(atom, zcore=z, potential=potential)
CALL get_gto_basis_set(orb_basis_set, &
nset=nset, nshell=nshell, npgf=npgf, lmin=lmin, lmax=lmax, l=ls, nsgf=nsgf, zet=zet, gcc=gcc, &
first_sgf=first_sgf, last_sgf=last_sgf)
NULLIFY (grid)
ngp = 400
quadtype = do_gapw_log
CALL allocate_grid_atom(grid)
CALL create_grid_atom(grid, ngp, 1, 1, 0, quadtype)
grid%nr = ngp
basis%grid => grid
NULLIFY (basis%am, basis%cm, basis%as, basis%ns, basis%bf, basis%dbf, basis%ddbf)
basis%basis_type = CGTO_BASIS
basis%eps_eig = 1.e-12_dp
! fill in the basis data structures
set_index = 0
shell_index = 0
basis%nprim = 0
basis%nbas = 0
DO i = 1, nset
DO j = lmin(i), MIN(lmax(i), lmat)
basis%nprim(j) = basis%nprim(j)+npgf(i)
END DO
DO j = 1, nshell(i)
l = ls(j, i)
IF (l <= lmat) THEN
basis%nbas(l) = basis%nbas(l)+1
k = basis%nbas(l)
CPASSERT(k <= 100)
set_index(l, k) = i
shell_index(l, k) = j
END IF
END DO
END DO
nj = MAXVAL(basis%nprim)
ns = MAXVAL(basis%nbas)
ALLOCATE (basis%am(nj, 0:lmat))
basis%am = 0._dp
ALLOCATE (basis%cm(nj, ns, 0:lmat))
basis%cm = 0._dp
DO j = 0, lmat
nj = 0
ns = 0
DO i = 1, nset
IF (j >= lmin(i) .AND. j <= lmax(i)) THEN
DO ipgf = 1, npgf(i)
basis%am(nj+ipgf, j) = zet(ipgf, i)
END DO
DO ii = 1, nshell(i)
IF (ls(ii, i) == j) THEN
ns = ns+1
DO ipgf = 1, npgf(i)
basis%cm(nj+ipgf, ns, j) = gcc(ipgf, ii, i)
END DO
END IF
END DO
nj = nj+npgf(i)
END IF
END DO
END DO
! Normalization as used in the atomic code
! We have to undo the Quickstep normalization
DO j = 0, lmat
prefac = 2.0_dp*SQRT(pi/dfac(2*j+1))
DO ipgf = 1, basis%nprim(j)
DO ii = 1, basis%nbas(j)
basis%cm(ipgf, ii, j) = prefac*basis%cm(ipgf, ii, j)
END DO
END DO
END DO
! initialize basis function on a radial grid
nr = basis%grid%nr
m = MAXVAL(basis%nbas)
ALLOCATE (basis%bf(nr, m, 0:lmat))