[molpro-user] state degeneracy - fundamental question

[Kirk Peterson]

Dear Amit,

it looks to me like you’ve forgotten to include many of the necessary degenerate states in your multi and ci, e.g., the triplet-S in symmetry 1, the Pz components of the P states, and I think 3 of the 5 for the D states.  This is why your degeneracies in multi are not perfect as well.

best regards,

-Kirk

> On Apr 24, 2016, at 6:27 AM, Amit Sharma <greifsw at gmail.com> wrote:
> 
> Hi All,
> I perform mcscf-ci-so atom calculation for np mp electrons (3p5 4p1 electronic configuration). The  2s+1-L-J atomic term symbols are triplet-D_3,2,1; triplet-P_2,1,0; triplet-S_1; singlet-D2; singlet-P1; singlet-S0 and we expect a total of 36 states in spin-orbit calculation plus the ground state which is singly degenerate.  The state averaging looks right and the  configurations generated in mcscf and ci are as expected. However, in spin orbit I only see 17 states (16+1).
> 
> Am I missing something here in my understanding or state counting? Also there are atomic term symbols like 3D_3 which should generate 7 degenerate states but I dont see that in SO output. Thanks in advance for your help/advice. Amit
> 
> ->> input
> 
>  ***, 3p5 4p1 
>  memory,100,m
>  gprint,orbitals,civector
> 
>  basis=avdz
>  geometry={Ar};
>  hf
>  multi
>  ci
>  hf
> !! D2h symmetry
>  {multi
>  occ,3,3,3,0,3,0,0,0
>  wf,18,1,2
>  wf,18,4,2
>  wf,18,6,2
>  wf,18,7,2
>  wf,18,1,0; state,2
>  wf,18,4,0
>  wf,18,6,0
>  wf,18,7,0
>  }
>  text, triplet ci calculation
>  {ci;wf,18,1,2;save,4012.2}; c1d=energd
>  {ci;wf,18,4,2;save,4042.2}; c2d=energd
>  {ci;wf,18,6,2;save,4062.2}; c3d=energd
>  {ci;wf,18,7,2;save,4072.2}; c4d=energd
>  text, singlet ci calculation
>  {ci;wf,18,1,0;state,2;save,4010.2}; c5d=energd
>  {ci;wf,18,4,0;save,4040.2}; c6d=energd
>  {ci;wf,18,6,0;save,4060.2}; c7d=energd
>  {ci;wf,18,7,0;save,4070.2}; c8d=energd
>  list
> {ci;hlsmat,ls,4012.2,4042.2,4062.2,4072.2, 4010.2,4040.2,4060.2, 4070.2}
> 
> 
> -- SO output
>    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   -526.96014612     -0.00000000       -0.00      0.00000000        0.00      0.0000
>    2   1   -526.46448743      0.49565868   108784.51      0.49565868   108784.51     13.4876
>    3   1   -526.46308779      0.49705833   109091.69      0.49705833   109091.69     13.5256
>    4   1   -526.46181508      0.49833104   109371.02      0.49833104   109371.02     13.5603
>    5   1   -526.45672447      0.50342165   110488.28      0.50342165   110488.28     13.6988
> 
>    6   4   -526.47885339      0.48129273   105631.54      0.48129273   105631.54     13.0966
>    7   4   -526.46395213      0.49619399   108901.99      0.49619399   108901.99     13.5021
>    8   4   -526.46180154      0.49834458   109373.99      0.49834458   109373.99     13.5606
>    9   4   -526.45743885      0.50270727   110331.49      0.50270727   110331.49     13.6794
> 
>   10   6   -526.47885340      0.48129272   105631.54      0.48129272   105631.54     13.0966
>   11   6   -526.46394897      0.49619715   108902.69      0.49619715   108902.69     13.5022
>   12   6   -526.46180523      0.49834089   109373.18      0.49834089   109373.18     13.5605
>   13   6   -526.45744091      0.50270521   110331.04      0.50270521   110331.04     13.6793
> 
>   14   7   -526.47885338      0.48129274   105631.55      0.48129274   105631.55     13.0966
>   15   7   -526.46394039      0.49620573   108904.57      0.49620573   108904.57     13.5024
>   16   7   -526.46181480      0.49833131   109371.08      0.49833131   109371.08     13.5603
>   17   7   -526.45744684      0.50269928   110329.74      0.50269928   110329.74     13.6791
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