[molpro-user] Bug in spin-orbit calculation
ZOUWL
qcband at gmail.com
Thu Nov 26 02:49:37 CET 2015
Dear developers,
There may be a bug in the following spin-orbit calculation. The low-lying
1D, 3P, 3F, and 5F states of Ta+ are calculated at the CASSCF(4,6) level,
where the 5d6s orbitals are active. Group symmery used here is Ci, but the
results and errors are the same if D2h is used. All the calculations are
performed using the 2010 version. Input:
***,Ta+, SOC with ECP
memory,100,m
symmetry,xyz
geometry={Ta}
basis=vtz-pp
{multi;natorb,ci;
frozen,0;closed,1,3;occ,7,3;
wf,12,1,0;state,5; ! 1D
wf,12,1,2;state,10; ! 3P, 3F
wf,12,1,4;state,7; ! 5F
}
{ci;noexc;wf,12,1,0;state,5;
save,4201.3;}
{ci;noexc;wf,12,1,2;state,10;
save,4221.3;}
{ci;noexc;wf,12,1,4;state,7;
save,4241.3;}
! SOC: singlet and triplet states
{ci;hlsmat,ecpls,4201.3,4221.3;}
! SOC: triplet and quintet states
{ci;hlsmat,ecpls,4221.3,4241.3;}
! SOC: singlet and quintet states
{ci;hlsmat,ecpls,4201.3,4241.3;}
---
The CASSCF energies of L-S states are degenerate (normal):
1D: -56.47502225 (x 5)
3P: -56.49919112 (x 3)
3F: -56.48533379 (x 7)
5F: -56.52492675 (x 7)
In the first (singlet + triplet) and the third (singlet + quintet) SOC
calculations, the energies of atomic J terms are degenerate (normal):
Nr Sym E E-E0 E-E0 E-E(1)
E-E(1) E-E(1)
(au) (au) (cm-1) (au)
(cm-1) (eV)
1 1 -56.51000193 -0.01081081 -2372.70 0.00000000
0.00 0.0000
2 1 -56.50459652 -0.00540540 -1186.35 0.00540540
1186.35 0.1471
3 1 -56.50459652 -0.00540540 -1186.35 0.00540540
1186.35 0.1471
4 1 -56.50459652 -0.00540540 -1186.35 0.00540540
1186.35 0.1471
5 1 -56.50158234 -0.00239123 -524.81 0.00841958
1847.88 0.2291
6 1 -56.50158234 -0.00239123 -524.81 0.00841958
1847.88 0.2291
7 1 -56.50158234 -0.00239123 -524.81 0.00841958
1847.88 0.2291
8 1 -56.50158234 -0.00239123 -524.81 0.00841958
1847.88 0.2291
9 1 -56.50158234 -0.00239123 -524.81 0.00841958
1847.88 0.2291
10 1 -56.49671921 0.00247191 542.52 0.01328272
2915.22 0.3614
11 1 -56.49671921 0.00247191 542.52 0.01328272
2915.22 0.3614
12 1 -56.49671921 0.00247191 542.52 0.01328272
2915.22 0.3614
13 1 -56.49671921 0.00247191 542.52 0.01328272
2915.22 0.3614
14 1 -56.49671921 0.00247191 542.52 0.01328272
2915.22 0.3614
...
Nr E E-E0 E-E0 E-E(1) E-E(1)
E-E(1)
(au) (au) (cm-1) (au) (cm-1)
(eV)
1 -56.54141852 -0.01649177 -3619.53 0.00000000 0.00
0.0000
2 -56.54141852 -0.01649177 -3619.53 0.00000000 0.00
0.0000
3 -56.54141852 -0.01649177 -3619.53 0.00000000 0.00
0.0000
4 -56.53729558 -0.01236883 -2714.64 0.00412294 904.88
0.1122
5 -56.53729558 -0.01236883 -2714.64 0.00412294 904.88
0.1122
6 -56.53729558 -0.01236883 -2714.64 0.00412294 904.88
0.1122
7 -56.53729558 -0.01236883 -2714.64 0.00412294 904.88
0.1122
8 -56.53729558 -0.01236883 -2714.64 0.00412294 904.88
0.1122
9 -56.53111117 -0.00618441 -1357.32 0.01030736 2262.20
0.2805
10 -56.53111117 -0.00618441 -1357.32 0.01030736 2262.20
0.2805
11 -56.53111117 -0.00618441 -1357.32 0.01030736 2262.20
0.2805
12 -56.53111117 -0.00618441 -1357.32 0.01030736 2262.20
0.2805
13 -56.53111117 -0.00618441 -1357.32 0.01030736 2262.20
0.2805
14 -56.53111117 -0.00618441 -1357.32 0.01030736 2262.20
0.2805
15 -56.53111117 -0.00618441 -1357.32 0.01030736 2262.20
0.2805
...
However, in the second SOC calculation (triplet + quintet), spherical
degeneracy (degeneracy = J * 2 + 1) is broken because of unknown reasons:
Nr E E-E0 E-E0 E-E(1) E-E(1)
E-E(1)
(au) (au) (cm-1) (au) (cm-1)
(eV)
1 -56.54145102 -0.01652427 -3626.66 0.00000000 0.00
0.0000
2 -56.54145075 -0.01652400 -3626.60 0.00000027 0.06
0.0000
3 -56.54144331 -0.01651655 -3624.96 0.00000771 1.69
0.0002
4 -56.53734340 -0.01241665 -2725.14 0.00410762 901.52
0.1118
5 -56.53734093 -0.01241418 -2724.60 0.00411009 902.06
0.1118
6 -56.53731961 -0.01239286 -2719.92 0.00413141 906.74
0.1124
7 -56.53730864 -0.01238189 -2717.51 0.00414238 909.15
0.1127
8 -56.53730809 -0.01238134 -2717.39 0.00414293 909.27
0.1127
9 -56.53118445 -0.00625770 -1373.41 0.01026657 2253.25
0.2794
10 -56.53117231 -0.00624555 -1370.74 0.01027871 2255.92
0.2797
11 -56.53116127 -0.00623451 -1368.32 0.01028975 2258.34
0.2800
12 -56.53114109 -0.00621434 -1363.89 0.01030993 2262.77
0.2805
13 -56.53113027 -0.00620352 -1361.52 0.01032075 2265.14
0.2808
14 -56.53112879 -0.00620203 -1361.19 0.01032223 2265.47
0.2809
15 -56.53112337 -0.00619661 -1360.00 0.01032765 2266.66
0.2810
...
There is no such a problem in the following all-electron calculation, so
the error may be related to the ECPLS option.
***,Ta+, SOC with A.E.
memory,100,m
symmetry,xyz
geometry={Ta}
basis=vtz-dk
set dkroll=1
{hf;occ,21,19;wf,80,1,0}
{multi;natorb,ci;
! 4f5s5p are inactive
frozen,14,9;closed,15,19;occ,21,19;
wf,72,1,0;state,5; ! 1D
wf,72,1,2;state,10; ! 3P, 3F
wf,72,1,4;state,7; ! 5F
}
{ci;noexc;wf,72,1,0;state,5;
save,4201.3;}
{ci;noexc;wf,72,1,2;state,10;
save,4221.3;}
{ci;noexc;wf,72,1,4;state,7;
save,4241.3;}
lsint
{ci;hlsmat,ls,4201.3,4221.3;}
{ci;hlsmat,ls,4221.3,4241.3;}
{ci;hlsmat,ls,4201.3,4241.3;}
---
Best wishes,
Wenli
-------------- next part --------------
An HTML attachment was scrubbed...
URL: <http://www.molpro.net/pipermail/molpro-user/attachments/20151126/82cb26da/attachment.html>
More information about the Molpro-user
mailing list