# [molpro-user] SO calculation problem

Peterson, Kirk kipeters at wsu.edu
Wed Dec 21 19:50:48 CET 2016

```Dear Wanlu,

are you sure the ECP you used included the SO parameters and not just the scalar ones?

best,

-Kirk

On Dec 21, 2016, at 3:29 AM, Wanlu Li <wanluli0716 at gmail.com<mailto:wanluli0716 at gmail.com>> wrote:

Dear Molpro users,
Greetings!
I'm using MOLPRO 2012 to calculate the CASSCF/SO energies with the diagonalized values obtained from CASPT2 method, but I found that there is no SO splitting. This is a heavy molecule containing Bi and must have strong SO effect.

I used no symmetry for my system and the following is the input part:

e_00=-452.13474035  AU
e_11=-452.05801678  AU
e_21=-452.05807425  AU
e_31=-452.02400192  AU
e_41=-452.02400190  AU
e_51=-452.00717351  AU
e_61=-452.00717351  AU
e_71=-451.99405747  AU
e_81=-451.99405748  AU
e_91=-451.97235095  AU
e_101=-451.97235095  AU
e_13=-452.04062682 AU
e_23=-452.04062684 AU
e_33=-451.98432662 AU
e_43=-451.98427832 AU
e_53=-451.98427832 AU

{hf,maxit=300,orbprint=20;
wf,nelec=52,sym=1,spin=2,charge=-1;
start,2100.2;
!rotate,27.1,23.1,0;
save,2100.2;
!occ,9,2,2,0;
}

{MCSCF
occ,31
closed,21
WF,52,1,2
state,1
!start,2140.2
WF,51,1,1
state,10
WF,51,1,3
state,5
orbital,2140.2
pspace,0
maxit,39
{ITERATIONS;
DO,UNCOUPLE,1,TO,2; }
}

{ci;
occ,31
core,21
closed,21
WF,52,1,2;state,1;noexc;save 4000.2;maxiter,500,500;}

{ci;
occ,31
core,21
closed,21
WF,51,1,1;state,10;noexc;save 4001.2;maxiter,500,500;}

{ci;
occ,31
core,21
closed,21
WF,51,1,3;state,5;noexc;save 4002.2;maxiter,500,500;}

hlsdiag=[e_00,e_11,e_21,e_31,e_41,e_51,e_61,e_71,e_81,e_91,e_101,e_13,e_23,e_33,e_43,e_53]

{ci;
hlsmat,ecp,4000.2,4001.2,4002.2
print,hls=1,vls=0}

pop;

The SO results in the output are:

Spin-orbit eigenstates   (energies)
======================

Nr         E             E-E0         E-E0           E-E(1)      E-E(1)      E-E(1)
(au)            (au)        (cm-1)           (au)       (cm-1)        (eV)
1  -452.13474035     0.00000000        0.00      0.00000000        0.00      0.0000
2  -452.13474035     0.00000000        0.00      0.00000000        0.00      0.0000
3  -452.13474035     0.00000000        0.00      0.00000000        0.00      0.0000
4  -452.05807425     0.07666610    16826.26      0.07666610    16826.26      2.0862
5  -452.05807425     0.07666610    16826.26      0.07666610    16826.26      2.0862
6  -452.05801678     0.07672357    16838.88      0.07672357    16838.88      2.0878
7  -452.05801678     0.07672357    16838.88      0.07672357    16838.88      2.0878
8  -452.04062684     0.09411351    20655.53      0.09411351    20655.53      2.5610
9  -452.04062684     0.09411351    20655.53      0.09411351    20655.53      2.5610
10  -452.04062684     0.09411351    20655.53      0.09411351    20655.53      2.5610
11  -452.04062684     0.09411351    20655.53      0.09411351    20655.53      2.5610
12  -452.04062682     0.09411353    20655.53      0.09411353    20655.53      2.5610
13  -452.04062682     0.09411353    20655.53      0.09411353    20655.53      2.5610
14  -452.04062682     0.09411353    20655.53      0.09411353    20655.53      2.5610
15  -452.04062682     0.09411353    20655.53      0.09411353    20655.53      2.5610
16  -452.02400192     0.11073843    24304.28      0.11073843    24304.28      3.0133
17  -452.02400192     0.11073843    24304.28      0.11073843    24304.28      3.0133
18  -452.02400190     0.11073845    24304.28      0.11073845    24304.28      3.0133
19  -452.02400190     0.11073845    24304.28      0.11073845    24304.28      3.0133
20  -452.00717351     0.12756684    27997.69      0.12756684    27997.69      3.4713
21  -452.00717351     0.12756684    27997.69      0.12756684    27997.69      3.4713
22  -452.00717351     0.12756684    27997.69      0.12756684    27997.69      3.4713
23  -452.00717351     0.12756684    27997.69      0.12756684    27997.69      3.4713
24  -451.99405748     0.14068287    30876.32      0.14068287    30876.32      3.8282
25  -451.99405748     0.14068287    30876.32      0.14068287    30876.32      3.8282
26  -451.99405747     0.14068288    30876.32      0.14068288    30876.32      3.8282
27  -451.99405747     0.14068288    30876.32      0.14068288    30876.32      3.8282
28  -451.98432662     0.15041373    33012.00      0.15041373    33012.00      4.0930
29  -451.98432662     0.15041373    33012.00      0.15041373    33012.00      4.0930
30  -451.98432662     0.15041373    33012.00      0.15041373    33012.00      4.0930
31  -451.98432662     0.15041373    33012.00      0.15041373    33012.00      4.0930
32  -451.98427832     0.15046203    33022.60      0.15046203    33022.60      4.0943
33  -451.98427832     0.15046203    33022.60      0.15046203    33022.60      4.0943
34  -451.98427832     0.15046203    33022.60      0.15046203    33022.60      4.0943
35  -451.98427832     0.15046203    33022.60      0.15046203    33022.60      4.0943
36  -451.98427832     0.15046203    33022.60      0.15046203    33022.60      4.0943
37  -451.98427832     0.15046203    33022.60      0.15046203    33022.60      4.0943
38  -451.98427832     0.15046203    33022.60      0.15046203    33022.60      4.0943
39  -451.98427832     0.15046203    33022.60      0.15046203    33022.60      4.0943
40  -451.97235095     0.16238940    35640.35      0.16238940    35640.35      4.4188
41  -451.97235095     0.16238940    35640.35      0.16238940    35640.35      4.4188
42  -451.97235095     0.16238940    35640.35      0.16238940    35640.35      4.4188
43  -451.97235095     0.16238940    35640.35      0.16238940    35640.35      4.4188

We can see that the energies don't split at all, could anyone help me to solve this problem?