[molpro-user] SO calculation problem

Alexander Mitrushchenkov Alexander.Mitrushchenkov at u-pem.fr
Thu Dec 22 10:57:17 CET 2016


Dear Wanlu,

Please also note that (apart from being sure SO-ECP is included and not 
just scalar ECP; use gprint,basis) in case you mix ecp/all electron 
atoms in your molecule, you should use 'LS' and not 'ECP' as the 
spin-orbit type in hlsmat.

Best,

Alexander

Le 21/12/2016 à 12:29, Wanlu Li a écrit :
> 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?
>
> Thanks in advance,
> Wanlu Li
>
>
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-- 
Dr. Alexander Mitrushchenkov, IGR
Laboratoire de Modélisation et Simulation Multi Echelle
UMR 8208 CNRS
Université Paris-Est Marne-la-Vallée
5 Bd Descartes
77454 Marne la Vallée, Cedex 2, France

Phone:    +33(0)160957316
Fax:      +33(0)160957320
e-mail:   Alexander.Mitrushchenkov at u-pem.fr

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