[molpro-user] SO calculation problem

Wanlu Li wanluli0716 at gmail.com
Wed Dec 21 12:29:17 CET 2016


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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