Hi,
I am comparing DKH2 calculations from PSI4 with Molpro.
For the following inputs, I got from PSI4 (basis set obtained from https://www.basissetexchange.org/) and from Molpro energies above the convergence threshold:
molecule clbr {
0 1
Cl 0. 0. 0.
Br 0. 0. 2.136
}
basis mb {
[cc-pVTZ-DK-def]
spherical
Br 0
S 20 1.00
10639000.0000000 0.0001832
1593400.0000000 0.0005094
362610.0000000 0.0013353
102700.0000000 0.0032222
33501.0000000 0.0076707
12093.0000000 0.0182439
4715.9000000 0.0433826
1955.6000000 0.0991426
852.6100000 0.2010706
387.6700000 0.3191212
182.6800000 0.3179374
88.2450000 0.1406661
39.2630000 0.0138611
19.2340000 -0.0008414
9.4057000 0.0003982
4.1601000 -0.0002226
1.8995000 0.0000678
0.6047200 -0.0000338
0.3011400 0.0000221
0.1251500 -0.0000052
S 20 1.00
10639000.0000000 -0.0000591
1593400.0000000 -0.0001646
362610.0000000 -0.0004325
102700.0000000 -0.0010466
33501.0000000 -0.0025103
12093.0000000 -0.0060229
4715.9000000 -0.0146734
1955.6000000 -0.0347901
852.6100000 -0.0773387
387.6700000 -0.1442475
182.6800000 -0.1985461
88.2450000 -0.0726261
39.2630000 0.3809663
19.2340000 0.5761470
9.4057000 0.2033629
4.1601000 0.0112299
1.8995000 0.0010430
0.6047200 -0.0001708
0.3011400 0.0000729
0.1251500 -0.0000318
S 20 1.00
10639000.0000000 0.0000236
1593400.0000000 0.0000657
362610.0000000 0.0001726
102700.0000000 0.0004176
33501.0000000 0.0010031
12093.0000000 0.0024075
4715.9000000 0.0058916
1955.6000000 0.0140102
852.6100000 0.0316098
387.6700000 0.0600877
182.6800000 0.0872309
88.2450000 0.0324842
39.2630000 -0.2258144
19.2340000 -0.5093521
9.4057000 -0.1106266
4.1601000 0.7018218
1.8995000 0.5477988
0.6047200 0.0393571
0.3011400 -0.0089968
0.1251500 0.0019468
S 1 1.00
0.6047200 1.0000000
S 20 1.00
10639000.0000000 -0.0000072
1593400.0000000 -0.0000202
362610.0000000 -0.0000530
102700.0000000 -0.0001284
33501.0000000 -0.0003083
12093.0000000 -0.0007407
4715.9000000 -0.0018109
1955.6000000 -0.0043190
852.6100000 -0.0097329
387.6700000 -0.0186483
182.6800000 -0.0270679
88.2450000 -0.0105140
39.2630000 0.0747565
19.2340000 0.1753422
9.4057000 0.0399153
4.1601000 -0.3301097
1.8995000 -0.4463003
0.6047200 0.2957042
0.3011400 0.6810696
0.1251500 0.2785627
S 1 1.00
0.1251500 1.0000000
P 13 1.00
8676.5000000 0.0009606
2055.9000000 0.0050551
666.2300000 0.0234154
253.1000000 0.0841414
106.1200000 0.2229616
47.2420000 0.3880657
21.8250000 0.3534548
9.9684000 0.1085321
4.5171000 0.0042339
1.9982000 0.0016954
0.7098800 -0.0004284
0.2814500 0.0001980
0.1020400 -0.0000690
P 13 1.00
8676.5000000 -0.0003881
2055.9000000 -0.0020557
666.2300000 -0.0096085
253.1000000 -0.0355099
106.1200000 -0.0981287
47.2420000 -0.1828576
21.8250000 -0.1498313
9.9684000 0.1959655
4.5171000 0.5433698
1.9982000 0.3792448
0.7098800 0.0434121
0.2814500 -0.0040330
0.1020400 0.0017114
P 1 1.00
0.7098800 1.0000000
P 13 1.00
8676.5000000 0.0001001
2055.9000000 0.0005330
666.2300000 0.0024808
253.1000000 0.0092595
106.1200000 0.0255286
47.2420000 0.0486125
21.8250000 0.0376864
9.9684000 -0.0631036
4.5171000 -0.1878988
1.9982000 -0.1319307
0.7098800 0.2976662
0.2814500 0.5723946
0.1020400 0.3063896
P 1 1.00
0.1020400 1.0000000
D 9 1.00
403.8300000 0.0016248
121.1700000 0.0130068
46.3450000 0.0582881
19.7210000 0.1698577
8.8624000 0.3172628
3.9962000 0.3831152
1.7636000 0.2764135
0.7061900 0.0753432
0.2639000 0.0020696
D 1 1.00
0.7061900 1.0000000
D 1 1.00
0.2639000 1.0000000
F 1 1.00
0.5515000 1.0000000
Cl 0
S 15 1.00
456100.0000000 0.0002645
68330.0000000 0.0008905
15550.0000000 0.0029934
4405.0000000 0.0098871
1439.0000000 0.0315606
520.4000000 0.0903711
203.1000000 0.2134406
83.9600000 0.3646772
36.2000000 0.3377387
15.8300000 0.1006810
6.3340000 0.0030732
2.6940000 0.0010373
0.9768000 -0.0003695
0.4313000 0.0001520
0.1625000 -0.0000502
S 15 1.00
456100.0000000 -0.0000747
68330.0000000 -0.0002515
15550.0000000 -0.0008492
4405.0000000 -0.0028128
1439.0000000 -0.0091519
520.4000000 -0.0269903
203.1000000 -0.0699330
83.9600000 -0.1426906
36.2000000 -0.1978853
15.8300000 -0.0143283
6.3340000 0.5036507
2.6940000 0.5584234
0.9768000 0.0768656
0.4313000 -0.0080500
0.1625000 0.0022404
S 1 1.00
0.9768000 1.0000000
S 15 1.00
456100.0000000 0.0000226
68330.0000000 0.0000761
15550.0000000 0.0002572
4405.0000000 0.0008515
1439.0000000 0.0027786
520.4000000 0.0082052
203.1000000 0.0214933
83.9600000 0.0445276
36.2000000 0.0646680
15.8300000 0.0041911
6.3340000 -0.2092752
2.6940000 -0.4033247
0.9768000 0.0827071
0.4313000 0.7256082
0.1625000 0.3896193
S 1 1.00
0.1625000 1.0000000
P 9 1.00
663.3000000 0.0026741
156.8000000 0.0197715
49.9800000 0.0894991
18.4200000 0.2567502
7.2400000 0.4366374
2.9220000 0.3493206
1.0220000 0.0583589
0.3818000 -0.0045545
0.1301000 0.0022637
P 1 1.00
1.0220000 1.0000000
P 9 1.00
663.3000000 -0.0007253
156.8000000 -0.0053474
49.9800000 -0.0249761
18.4200000 -0.0730005
7.2400000 -0.1338923
2.9220000 -0.0940334
1.0220000 0.2627700
0.3818000 0.5640464
0.1301000 0.3413419
P 1 1.00
0.1301000 1.0000000
D 1 1.00
1.0460000 1.0000000
D 1 1.00
0.3440000 1.0000000
F 1 1.00
0.7060000 1.0000000
assign Cl cc-pVTZ-DK-def
assign Br cc-pVTZ-DK-def
}
basis mb2 {
[cc-pVTZ-DK-def-d]
spherical
Cl 0
S 1 1.00
456100.0000000 1.00000000D+00
S 1 1.00
68330.0000000 1.00000000D+00
S 1 1.00
15550.0000000 1.00000000D+00
S 1 1.00
4405.0000000 1.00000000D+00
S 1 1.00
1439.0000000 1.00000000D+00
S 1 1.00
520.4000000 1.00000000D+00
S 1 1.00
203.1000000 1.00000000D+00
S 1 1.00
83.9600000 1.00000000D+00
S 1 1.00
36.2000000 1.00000000D+00
S 1 1.00
15.8300000 1.00000000D+00
S 1 1.00
6.3340000 1.00000000D+00
S 1 1.00
2.6940000 1.00000000D+00
S 1 1.00
0.9768000 1.00000000D+00
S 1 1.00
0.4313000 1.00000000D+00
S 1 1.00
0.1625000 1.00000000D+00
P 1 1.00
663.3000000 1.00000000D+00
P 1 1.00
156.8000000 1.00000000D+00
P 1 1.00
49.9800000 1.00000000D+00
P 1 1.00
18.4200000 1.00000000D+00
P 1 1.00
7.2400000 1.00000000D+00
P 1 1.00
2.9220000 1.00000000D+00
P 1 1.00
1.0220000 1.00000000D+00
P 1 1.00
0.3818000 1.00000000D+00
P 1 1.00
0.1301000 1.00000000D+00
D 1 1.00
1.0460000 1.00000000D+00
D 1 1.00
0.3440000 1.00000000D+00
F 1 1.00
0.7060000 1.00000000D+00
Br 0
S 1 1.00
10639000.0000000 1.00000000D+00
S 1 1.00
1593400.0000000 1.00000000D+00
S 1 1.00
362610.0000000 1.00000000D+00
S 1 1.00
102700.0000000 1.00000000D+00
S 1 1.00
33501.0000000 1.00000000D+00
S 1 1.00
12093.0000000 1.00000000D+00
S 1 1.00
4715.9000000 1.00000000D+00
S 1 1.00
1955.6000000 1.00000000D+00
S 1 1.00
852.6100000 1.00000000D+00
S 1 1.00
387.6700000 1.00000000D+00
S 1 1.00
182.6800000 1.00000000D+00
S 1 1.00
88.2450000 1.00000000D+00
S 1 1.00
39.2630000 1.00000000D+00
S 1 1.00
19.2340000 1.00000000D+00
S 1 1.00
9.4057000 1.00000000D+00
S 1 1.00
4.1601000 1.00000000D+00
S 1 1.00
1.8995000 1.00000000D+00
S 1 1.00
0.6047200 1.00000000D+00
S 1 1.00
0.3011400 1.00000000D+00
S 1 1.00
0.1251500 1.00000000D+00
P 1 1.00
8676.5000000 1.00000000D+00
P 1 1.00
2055.9000000 1.00000000D+00
P 1 1.00
666.2300000 1.00000000D+00
P 1 1.00
253.1000000 1.00000000D+00
P 1 1.00
106.1200000 1.00000000D+00
P 1 1.00
47.2420000 1.00000000D+00
P 1 1.00
21.8250000 1.00000000D+00
P 1 1.00
9.9684000 1.00000000D+00
P 1 1.00
4.5171000 1.00000000D+00
P 1 1.00
1.9982000 1.00000000D+00
P 1 1.00
0.7098800 1.00000000D+00
P 1 1.00
0.2814500 1.00000000D+00
P 1 1.00
0.1020400 1.00000000D+00
D 1 1.00
403.8300000 1.00000000D+00
D 1 1.00
121.1700000 1.00000000D+00
D 1 1.00
46.3450000 1.00000000D+00
D 1 1.00
19.7210000 1.00000000D+00
D 1 1.00
8.8624000 1.00000000D+00
D 1 1.00
3.9962000 1.00000000D+00
D 1 1.00
1.7636000 1.00000000D+00
D 1 1.00
0.7061900 1.00000000D+00
D 1 1.00
0.2639000 1.00000000D+00
F 1 1.00
0.5515000 1.00000000D+00
assign Cl cc-pVTZ-DK-def-d
assign Br cc-pVTZ-DK-def-d
}
set {
reference rhf
relativistic dkh
dkh_order 2
scf_type pk
guess gwh
basis mb
basis_relativistic mb2
D_convergence 1e-10
E_convergence 1e-10
}
energy(โhfโ)
memory,120,m
gprint,basis
dkho=2
angstrom
geometry={
Cl 0. 0. 0.
Br 0. 0. 2.136
}
wf,charge=0,spin=0
gthresh,energy=1.d-10
basis,cl=cc-pVTZ-DK, br=cc-pVTZ-DK
{hf
}
{ccsd(t)}
psi-4 1.7 -3065.2229486335891124
molpro 2022 -3065.222943870092
the difference (5*10^-6) is above the convergence threshold (10^(-10))
My questions are:
- What is the reason for this energy difference above the convergence threshold?
- What is the reason that PSI4 spends much more time than molpro (about a factor of 20, for more electron systems, the difference is larger)? Is that due to handling of general contracted basis? Density-fitting would be faster. But, will the default, def2-universal-jkfit, suitable for basis set optimized for DKH? In Auxiliary Basis Sets, there is not an auxiliary basis for DK basis.
- Why in PSI4 one needs to prepare an uncontracted auxiliary basis for DKH as in Scalar relativistic Hamiltonians?
Thank you very much
P.S. seems four asterisks after a basis set disappeared in this post