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tumitumi123

Member

Registered: 2017-06-13

Posts: 16

transition dipole for spin-orbit eigenfunction using RASSI

Dear all,

I am trying to calculate the transition dipole for CH3I along CI distance, which has already been studied for a long time. First I use CASSCF to optimize the geometry at every CI distance,  then do MS-CASPT2 and RASSI to get the potential curve and dipole. The curve looks correct compare with literature, but the transition dipoles are very strange, at least 4 times smaller than other's dataa. Can anyone give me any suggestions about this?  Another thing I don't understand is that now the transition dipole is complex numbers in spin-orbit states? Below is the input file and part of the output.

Any suggestion is welcomed.
Thanks very much.

Shan

input:

&gateway
coord
5
Angstrom
C1    0 0 $cz
H1   $h1x $h1y $h1z
H2 $h2x $h2y $h2z
H3 $h3x $h3y $h3z 
I1   0   0   $RCI
basis=ano-rcc-vdzp
group=nosymm
&seward
&RASSCF
spin=1
nactel=6 0 0
inactive=28
ras2=4
ciroot=3 3 1
symmetry=1
>> COPY $WorkDir/xue.JobIph $WorkDir/JOBOLD
&caspt2
multistate
3 1 2 3 
>> COPY $WorkDir/xue.JobMix $WorkDir/JOB001

&RASSCF
JOBIPH
cionly
spin=3
nactel=6 0 0
inactive=28
ras2=4
ciroot=3 3 1
symmetry=1
 
&caspt2
multistate
3 1 2 3    
>> COPY $WorkDir/xue.JobMix $WorkDir/JOB002

&rassi
Nrof
2 3 3
1 2 3
1 2 3   
spin orbital
meso
ejob

output:

      ****************************************************************************************************
      *                                                                                                  *
      *                                  Spin-orbit properties section                                   *
      *                                                                                                  *
      ****************************************************************************************************


++ Matrix Elements over SO states

  =========================================
   MATRIX ELEMENTS OF 1-ELECTRON OPERATORS
   FOR THE SPIN-ORBIT EIGENSTATES:
  =========================================

  SELECTED PROPERTIES:
 MLTPL  1  1    MLTPL  1  2    MLTPL  1  3


 PROPERTY: MLTPL  1   COMPONENT:   1

  STATE                1                                     2
    1  (-0.231055028E-05,-0.190429760E-22)   ( 0.518972626E-05, 0.449517974E-05)
    2  ( 0.518972626E-05,-0.449517974E-05)   ( 0.417565681E-03,-0.346944695E-17)
    3  (-0.312178927E-02,-0.738072231E-03)   ( 0.301679112E-07, 0.416803840E-07)
    4  (-0.441893781E-01, 0.469273024E-03)   ( 0.110456551E-04, 0.942143065E-05)
    5  ( 0.105872051E-02, 0.470273443E-03)   ( 0.253889348E-03, 0.544655907E-03)
    6  (-0.725882119E-08, 0.253493189E-07)   ( 0.371623660E-01,-0.240979185E-01)
    7  (-0.921502098E-05,-0.414849392E-05)   ( 0.392479087E-04, 0.846760919E-04)
    8  (-0.393748553E-02, 0.151727264E-02)   (-0.158193113E-02,-0.575262774E-03)
    9  (-0.120088829    , 0.103854532E-02)   ( 0.478549726E-04, 0.409478562E-04)
   10  ( 0.490826072E-09,-0.111023962E-08)   (-0.384419392E-02, 0.180023017E-02)
   11  (-0.324182731E-03, 0.247088393E-03)   ( 0.159634067E-01, 0.104436141E-02)
   12  ( 0.711046035E-02,-0.619156267E-02)   ( 0.728367150E-03, 0.191560268E-07)