UKS density fitting gradient problem

[baopengbp]

For small molecules, the UKS density fitting gradient is OK.
There is a problem of UKS density fitting gradient when I compute T1 state of PXZ-DPS. The direct SCF is OK.

import time
import pyscf
from pyscf.geomopt.geometric_solver import optimize
from gpu4pyscf.dft import uks

atom = '''
O +0.285437 -4.158343 -1.632910
S +0.230926 -3.572487 -0.284556
O +0.267242 -4.402410 +0.929598
C -1.261603 -2.562902 -0.199664
C -1.826445 -2.281078 +1.045687
C -2.973056 -1.491629 +1.107457
C -3.554131 -1.000794 -0.068718
N -4.729283 -0.193145 -0.000034
C -4.640771 +1.208548 -0.146767
C -3.430281 +1.876262 -0.362100
C -3.393085 +3.267620 -0.498501
C -4.563859 +4.014070 -0.416526
C -5.778681 +3.359783 -0.191313
C -5.814869 +1.979404 -0.055388
O -7.049528 +1.409454 +0.181427
C -7.128768 +0.036190 +0.304534
C -8.390286 -0.501583 +0.515176
C -8.553959 -1.884360 +0.640237
C -7.441461 -2.713968 +0.545168
C -6.170448 -2.171222 +0.331657
C -5.992092 -0.788446 +0.217106
C -2.986770 -1.308869 -1.311579
C -1.833953 -2.088990 -1.381507
C +1.582607 -2.384116 -0.161074
C +2.092824 -1.805784 -1.324951
C +3.129600 -0.880169 -1.224150
C +3.656852 -0.547631 +0.030172
N +4.718807 +0.401567 +0.129316
C +6.045702 +0.021726 -0.171840
C +6.399375 -1.283509 -0.529908
C +7.728181 -1.612246 -0.816074
C +8.724032 -0.643817 -0.742912
C +8.384707 +0.661758 -0.375571
C +7.066115 +0.987218 -0.092130
O +6.811949 +2.294113 +0.275159
C +5.512721 +2.654506 +0.571060
C +5.297004 +3.976122 +0.934312
C +4.007033 +4.422013 +1.237474
C +2.943197 +3.528792 +1.166631
C +3.161207 +2.196814 +0.800240
C +4.448525 +1.735795 +0.504209
C +3.147228 -1.150993 +1.186608
C +2.103668 -2.070407 +1.095472
H -1.380310 -2.686415 +1.947647
H -3.429702 -1.254793 +2.063372
H -2.510236 +1.306253 -0.422062
H -2.438273 +3.756918 -0.667348
H -4.543268 +5.094304 -0.522267
H -6.714066 +3.905063 -0.113910
H -9.232681 +0.180254 +0.576377
H -9.543644 -2.298454 +0.806211
H -7.547883 -3.791180 +0.632326
H -5.312597 -2.829089 +0.251726
H -3.458152 -0.937827 -2.216294
H -1.396909 -2.353523 -2.338490
H +1.691399 -2.089194 -2.292115
H +3.541925 -0.413711 -2.113434
H +5.633620 -2.048948 -0.583442
H +7.971683 -2.633693 -1.092955
H +9.757611 -0.891531 -0.963938
H +9.131961 +1.445495 -0.300399
H +6.153619 +4.641790 +0.971286
H +3.845981 +5.457249 +1.521843
H +1.932732 +3.856216 +1.393217
H +2.323315 +1.511432 +0.743362
H +3.577920 -0.897804 +2.150333
H +1.714440 -2.561770 +1.980825
'''

mol = pyscf.M(atom=atom, spin=2, verbose=4, basis='def2-svp')
mf_GPU = uks.UKS(mol, xc='pbe0').density_fit()
#mf_GPU.disp = 'd3bj'
mf_GPU.grids.level = 3
mf_GPU.conv_tol = 1e-10
mf_GPU.max_cycle = 50

gradients = []
def callback(envs):
gradients.append(envs['gradients'])

start_time = time.time()
mol_eq = optimize(mf_GPU, maxsteps=50, callback=callback)
print("Optimized coordinate:")
print(mol_eq.atom_coords())
print('geometry optimization took', time.time() - start_time, 's')

The first DF gradient is:
converged SCF energy = -2191.1017687459 <S^2> = 2.018467 2S+1 = 3.0122862
--------------- DFUKS_Scanner gradients ---------------
x y z
0 O 0.0074075928 -0.0503701331 -0.1719910994
1 S 0.0040317954 -0.0463937330 0.0015015689
2 O 0.0015702868 -0.0801459516 0.1535435516
3 C 0.0802308384 -0.0293312424 0.0052545674
4 C -0.0194108000 0.0360821960 -0.0209733619
5 C 0.0037590661 -0.0143464518 0.0094371372
6 C -0.1147167540 0.0811413498 -0.0044039285
7 N 0.0467878655 -0.0258417215 -0.0045235079
8 C 0.0267182992 -0.0434278328 -0.0034430772
9 C -0.0183804654 0.0733211379 -0.0061551308
10 C 0.0018592585 -0.0010985513 -0.0004807828
11 C 0.0058123946 0.0384863958 -0.0051844576
12 C 0.0379732540 0.0105343296 -0.0054599896
13 C -0.0159434997 -0.0239168028 0.0062611757
14 O -0.1389620408 0.0960588850 0.0124048450
15 C 0.0200882968 0.0147833717 -0.0051837819
16 C -0.0065348166 -0.0286815671 0.0024679537
17 C -0.0282689082 -0.0148146968 0.0046516281
18 C -0.0015123931 -0.0009493365 0.0013643065
19 C -0.0734410099 -0.0264017982 0.0118577282
20 C 0.0432248562 -0.0144950575 -0.0022850391
21 C 0.0181673027 -0.0165785283 0.0160831174
22 C -0.0379605328 0.0240640691 0.0047592392
23 C -0.0983847779 -0.0459888622 -0.0166751323
24 C 0.0254661277 0.0404841340 0.0040395884
25 C -0.0204965652 -0.0250883116 0.0215996992
26 C 0.1157057969 0.0894194189 -0.0061293362
27 N -0.0535343579 -0.0208546606 0.0156041026
28 C -0.0637138136 -0.0258228584 -0.0027358795
29 C 0.0902193783 -0.0399946056 -0.0199638283
30 C -0.0486303048 0.0264612128 0.0129992616
31 C 0.0902421292 -0.0392002973 -0.0220331589
32 C -0.0165067011 -0.0395580200 -0.0061180450
33 C -0.0013079658 0.0054221589 0.0033991221
34 O 0.1391237316 0.1138225607 0.0078804042
35 C 0.0352604310 -0.0314912922 -0.0196584156
36 C -0.0381633480 0.0101944878 0.0087992262
37 C -0.0085275428 0.0212763993 0.0072661771
38 C -0.0112760363 0.0123768284 0.0057945253
39 C 0.0144640296 0.0737962720 0.0189795611
40 C -0.0070867268 -0.0194548755 -0.0030321733
41 C -0.0194678643 -0.0181957506 -0.0181578436
42 C 0.0443685354 0.0328341163 0.0102553187
43 H 0.0429839580 -0.0346677751 0.0778138044
44 H -0.0303236695 0.0164181285 0.0697499481
45 H 0.0780892394 -0.0510984559 -0.0040445547
46 H 0.0596996149 0.0232971339 -0.0095224399
47 H 0.0024405730 0.0531711682 -0.0050154021
48 H -0.0520481668 0.0304546703 0.0042639604
49 H -0.0433026077 0.0350983541 0.0033698180
50 H -0.0449383523 -0.0197625124 0.0077542623
51 H -0.0003922228 -0.0572015427 0.0039961452
52 H 0.0712166541 -0.0483077630 -0.0067564397
53 H -0.0295241753 0.0259953636 -0.0624230344
54 H 0.0434795801 -0.0228706507 -0.0813219565
55 H -0.0379667294 -0.0238553072 -0.0874196004
56 H 0.0282729418 0.0342562643 -0.0672397236
57 H -0.0695257650 -0.0473753486 -0.0010689875
58 H -0.0002752048 -0.0387971245 -0.0105449873
59 H 0.0409643134 -0.0099092389 -0.0090965931
60 H 0.0418629297 0.0427952386 0.0039020976
61 H 0.0447567651 0.0344602075 0.0017526412
62 H -0.0098864992 0.0522136486 0.0144307813
63 H -0.0642553635 0.0142715942 0.0122937144
64 H -0.0727871638 -0.0636377303 -0.0069593920
65 H 0.0289963256 0.0189154691 0.0726663106
66 H -0.0377910165 -0.0419801772 0.0778037916

cycle 1: E = -2191.10176875 dE = -2191.1 norm(grad) = 0.634282

The first direct SCF gradient is:
converged SCF energy = -2191.10167913584 <S^2> = 2.0184678 2S+1 = 3.0122867
--------------- UKS_Scanner gradients ---------------
x y z
0 O 0.0000589797 -0.0020283862 -0.0044643884
1 S 0.0023232417 -0.0234694406 -0.0022217418
2 O -0.0000798197 -0.0028428101 0.0039975683
3 C -0.0292135918 0.0251439531 0.0020938915
4 C 0.0176947792 -0.0126095710 -0.0082209816
5 C -0.0138355558 0.0093479746 -0.0050732578
6 C 0.0074208103 -0.0053285710 -0.0002892279
7 N 0.0101116936 -0.0069052585 -0.0005936181
8 C 0.0047754503 0.0204218459 -0.0029803329
9 C -0.0022485576 -0.0086507975 0.0011871361
10 C 0.0019317294 0.0110313397 -0.0013287699
11 C 0.0072377519 0.0057377319 -0.0013898621
12 C -0.0052670010 -0.0020981272 0.0007884839
13 C 0.0180831883 0.0028248569 -0.0023242172
14 O -0.0169069268 0.0115053446 0.0018625539
15 C 0.0039939138 -0.0177333374 0.0003265314
16 C -0.0000669306 0.0057102593 -0.0004549480
17 C -0.0027104704 -0.0090173251 0.0009209961
18 C -0.0095573359 -0.0057562032 0.0017524748
19 C 0.0073325479 0.0050546262 -0.0016888093
20 C -0.0168259578 -0.0117877542 0.0037000098
21 C -0.0152754499 0.0063152947 0.0064387731
22 C 0.0179713610 -0.0133860071 0.0059748331
23 C 0.0247647732 0.0277988136 0.0030211265
24 C -0.0152698229 -0.0153873793 0.0049255202
25 C 0.0121391512 0.0093356275 0.0061492144
26 C -0.0062746949 -0.0056216626 -0.0010573771
27 N -0.0089202957 -0.0083418948 0.0000634973
28 C 0.0178370474 -0.0083042255 -0.0054659610
29 C -0.0078137783 0.0033436497 0.0022347806
30 C 0.0098710979 -0.0041620596 -0.0025322538
31 C 0.0038699142 -0.0080439797 -0.0024335022
32 C -0.0004816722 0.0055205111 0.0014096873
33 C -0.0016501936 -0.0173621737 -0.0036462913
34 O 0.0151404677 0.0133389271 0.0009830687
35 C -0.0180011822 0.0000727207 0.0022602012
36 C 0.0055467872 -0.0010364757 -0.0010081883
37 C -0.0076877197 0.0044349570 0.0021473454
38 C -0.0034433276 0.0100056842 0.0030486470
39 C 0.0029653646 -0.0078707215 -0.0025169260
40 C -0.0071010064 0.0185879786 0.0058874925
41 C 0.0136287924 0.0088034167 -0.0041662572
42 C -0.0156137721 -0.0137375742 -0.0080674338
43 H -0.0014838248 0.0024453439 -0.0038018287
44 H 0.0017180287 -0.0004499344 -0.0051747528
45 H -0.0030067918 0.0044371839 0.0001178975
46 H -0.0036014867 -0.0016666619 0.0006404832
47 H 0.0000849892 -0.0042854289 0.0004001802
48 H 0.0036835282 -0.0020841253 -0.0004145359
49 H 0.0032796221 -0.0027076167 -0.0001373006
50 H 0.0039668085 0.0015222847 -0.0006302233
51 H 0.0002339378 0.0040557235 -0.0002551677
52 H -0.0051850560 0.0012939599 0.0004864194
53 H 0.0019504105 -0.0009659681 0.0050344690
54 H -0.0013305502 0.0020356480 0.0041500510
55 H 0.0012317026 0.0018973455 0.0041948574
56 H -0.0016248589 -0.0016314137 0.0049236994
57 H 0.0049101551 0.0020376353 -0.0001556143
58 H -0.0007634216 0.0038842146 0.0009841493
59 H -0.0041224436 0.0008704182 0.0008375188
60 H -0.0028947499 -0.0030953583 -0.0003928794
61 H -0.0033938971 -0.0025675882 -0.0000473094
62 H 0.0004794815 -0.0041332023 -0.0011082054
63 H 0.0037949352 -0.0010735427 -0.0008312491
64 H 0.0024281998 0.0046860346 0.0006941415
65 H -0.0018626594 -0.0003046733 -0.0051060953
66 H 0.0010541608 0.0029459449 -0.0036581919

cycle 1: E = -2191.10167914 dE = -2191.1 norm(grad) = 0.113575

[wxj6000]

The issue has been fixed in
#226