Enquiry: spin-orbit calculation for diatomic molecules and spin orbit transition moments

Fri Jun 8 05:18:20 BST 2001

To all Molpro Experts


SUBJECT : spin-orbit calculation for diatomic molecules and spin orbit transition moments


Dear MOLPRO Experts

        Now I am trying to calculate the electronic energy surfaces of Alkali Dimers (like KRb, Rb2,RbCs etc.). My aim is to calculate electronic surfaces of molecule with full spin-orbit interactions. Finally I want to get the Transition moments between different electronic states of the diatomic molecule. Now I have KRb potentials are calculating corectly without spin-orbt interactions only. I welcome any help from you to help me to include spin-orbit interactions in this molecular calculations and also help me to calculate the spin-orbit transition moments between different electronic states of the molecule. I am using Stuttgart ECP basis, spin-orbit basis is not available and I have not much idea in it!. 

       I am including my input below.

       With thanks to you all

-------------------------------------------
Dr. Avijit Datta, Ph.D
Post Doctoral Fellow
Department of Chemistry
Korea Advanced Institute of Science and Technology
Taejon- 305-701, Korea
Email: adatta at alkali.kaist.ac.kr
-------------------------------------------


MOLPRO input
-------------------------------------


***, KRb(9s9p6d1f)
  
memory,5,m;
  
 file,1,krb1s.int!;
 file,2,yjchoite.orb ;
  
 Rs = [ 2.20, 3.0, 4.0 ], ang;

gprint,basis;
gprint,orbital;


 geometry={a1,K}
 basis={
 s,K,  8.223362, 3.797211, 1.331607, 0.666282, 0.272807, 0.037092, 0.016543,0.0079000, 0.003900;
 p,K, 21.605670, 1.100212, 0.504345, 0.257869, 0.148150, 0.085000, 0.043380,0.0083275, 0.00429649;
 d,K,  4.306440, 1.048700, 0.279734, 0.0704566,0.0230622,0.0087089;
 f,K,   1.119;

ecp,K,10,4,1;     ! I think S-O  term should be included here. no idea about spin basis. 
 1;
 2, 1.00000000,  0.00000000;
 1;
 2, 6.84380700, 92.25263900;
 1;
 2, 4.21785700, 23.49803500;
 2;
 2, 6.49753700, -7.31542000;
 2, 1.00753700,  0.52282739;
 1;
 2, 6.12361300, -3.85832000;
 }
  
int;
rhf-scf;
 occ,2,1,1,0,1,0,0,0;
 wf,9,1,1;
 orbital,2101.2;
 
data,nen,1;

 geometry={a1,Rb}
 basis={
 s,Rb, 4.727461, 2.930825, 0.601849, 0.466244, 0.246463, 0.135694, 0.0254318,0.005929, 0.0025920;
 p,Rb, 5.608470, 3.430270, 0.767394, 0.345439, 0.156369, 0.0360405,0.0187985,0.0105292,0.00665991;
 d,Rb, 0.751276, 0.331169, 0.096302, 0.029860, 0.0150183,0.008028;
 f,Rb, 0.8075;
 
ecp,Rb,28,4,1;    ! I think S-O  term should be included here. no idea about spin basis. 
 1;
 2, 1.00000000,  0.00000000;
 2;
 2, 5.03655181, 89.50019822;
 2, 1.97084963,  0.49376198;
 2;
 2, 4.25834119, 58.56897492;
 2, 1.47070961,  0.43179108;
 3;
 2, 4.07726521, 11.95313706;
 2, 0.72613556,  0.96810247;
 2, 0.81094068,  0.72729813;
 1;
 2, 3.84311471,-12.31690065;
 
 }
 
int;
rhf-scf;
 occ,2,1,1,0,1,0,0,0;
 wf,9,1,1;
 orbital,2102.2;
 
 
data,nen,1;
 
geometry={K;
          Rb,K,R;}
 
 
do i =1,#Rs
 
R = Rs(i);
 
 basis={
  s,K,  8.223362, 3.797211, 1.331607, 0.666282, 0.272807, 0.037092, 0.016543,0.0079000, 0.003900;
 p,K, 21.605670, 1.100212, 0.504345, 0.257869, 0.148150, 0.085000, 0.043380,0.0083275, 0.00429649;
 d,K,  4.306440, 1.048700, 0.279734, 0.0704566,0.0230622,0.0087089;
 f,K,   1.119;

 s,Rb, 4.727461, 2.930825, 0.601849, 0.466244, 0.246463, 0.135694, 0.0254318,0.005929, 0.0025920;
 p,Rb, 5.608470, 3.430270, 0.767394, 0.345439, 0.156369, 0.0360405,0.0187985,0.0105292,0.00665991;
 d,Rb, 0.751276, 0.331169, 0.096302, 0.029860, 0.0150183,0.008028;
 f,Rb,  0.8075;

 ecp,K,10,4,1;
 1;
 2, 1.00000000,  0.00000000;
 1;
 2, 6.84380700, 92.25263900;
 1;
 2, 4.21785700, 23.49803500;
 2;
 2, 6.49753700, -7.31542000;
 2, 1.00753700,  0.52282739;
 1;
 2, 6.12361300, -3.85832000;
 
 ecp,Rb,28,4,1;
 1;
 2, 1.00000000,  0.00000000;
 2;
 2, 5.03655181, 89.50019822;
 2, 1.97084963,  0.49376198;
 2;
 2, 4.25834119, 58.56897492;
 2, 1.47070961,  0.43179108;
 3;
 2, 4.07726521, 11.95313706;
 2, 0.72613556,  0.96810247;
 2, 0.81094068,  0.72729813;
 1;
 2, 3.84311471,-12.31690065;
 }
 
int;
rhf-scf;
 occ,5,2,2,0;
 save,2103.2;
 wf,18,1,0;
maxiter=100
 escf(i)=energy;
 
merge,2104.2;
 orbital,2101.2;
 move,1.1,1.1,1.1,0,1.0,1,9;                                                    ! K  3s
 move,1.2,1.2,2.1,9,1.0,1,9;                                                    ! K  3pz
 
 orbital,2102.2;offset,0,0,0,0;
 move,1.1,1.1,3.1,32,1.0,1,9;                                                   ! Rb 4s
 move,1.2,1.2,4.1,41,1.0,1,9;                                                   ! Rb 4pz
 
 orbital,2101.2;offset,0,0,0,0;
 move,1.2,1.2,1.2,0,1.0,1,9;                                                    ! K  3px
 
 orbital,2102.2;offset,0,0,0,0;
 move,1.2,1.2,2.2,17,1.0,1,9;                                                   ! Rb 4px
 
 orbital,2101.2;offset,0,0,0,0;
 move,1.3,1.3,1.3,0,1.0,1,9;                                                    ! K  3py
 
 orbital,2102.2;offset,0,0,0,0;
 move,1.3,1.3,2.3,17,1.0,1,9;                                                   ! Rb 4py
 
 schmidt,3,1,1,0;

 orbital,2103.2;
 add,5.1,,5.1;
 add,3.2,,3.2;
 add,3.3,,3.3;
 add,1.4,,1.4;
 
cpp,init,-2;
 K,2,5.354,,,0.5412677992,1.;
 Rb,2,8.670,,,0.3569968363,1.;
 cpp,ae,2104.2;
 core,4,2,2,0;

multi;
 occ,16,4,4,0;
 closed,4,2,2,0;
 core,4,2,2,0,2104.2;
 wf,18,2,2;state,5;
 orbital,2140.2;
 maxiter,100;

mrci;
 occ,16,4,4,0;
 core,4,2,2,0;
 closed,4,2,2,0;
 orbit,2140.2;
 wf,18,2,2;state,1;
 noexc;
 save,7100.1;
 dm,2206.2;
 maxiter,100;
! esic1(1)=energy(1);

multi;
 occ,16,4,4,0;
 closed,4,2,2,0;
 core,4,2,2,0,2104.2;
 wf,18,2,0;state,5;
 orbital,2141.2;
 maxiter,100;

mrci;
 occ,16,4,4,0;
 core,4,2,2,0;
 closed,4,2,2,0;
 orbit,2141.2;
 wf,18,2,0;state,1;
 noexc;
 save,7300.1;
 dm,2207.2;
 maxiter,100;
! esic2(1)=energy(1);

LSINT;Z;
mrci;
HLSMAT,LS,7100.1,7100.1;
enddo
! table,Rs,spinor
! head, Rs,SOmoment
! save 1sig.tab;
---;
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