Posted by Chaehyuk Ko on October 23, 2005 at 04:10:37:
I have done a MSPT2 calculation, where RASSI was done at the end of calculation. It seems that the oscillator strengths between the various states were obtained at the CASSCF level. To obtain the offdiagonal dipole moment matrix in x ,y , and z component, respectively, I used the Einstein coefficient Ax,Ay,and Az, which are printed next to the oscillator strength. The values obtained from A coeff's do not agree with the corresponding oscillator strength in the output. Actually I got a transition dipole moment of 30 Debye(too large!!!). Below are the output of RASSI. I used CASSCF energy to calculate the transition dipole moments(thus oscillator strength.). The oscillator strength agrees with the result of other CASSCF code.
In short, I can not get the printed value of oscillator strength from the Einstein coefficients.
Any suggestion would be appreciated.
To From Osc. Ax, Ay, Az
1 2 1.04E-06 9128.7387 5.7601965 2.2408172
1 3 1.683336 292.29188 9.76E+09 6.01E+09
1 4 8.11E-02 26.454901 3.02E+08 7.27E+08
1 5 2.93E-02 9.5134513 22640738 3.77E+08
2 3 7.24E-08 39.37399 1.79E-02 6.46E-03
2 4 3.80E-07 1466.9033 1.42E-02 3.16E-03
2 5 7.71E-05 371467.15 0.1770263 1.33E-03
3 4 6.92E-04 3.87E-02 356416.15 1940276.5
3 5 1.82E-02 5.94E-02 10824609 66737565
4 5 8.23E-04 1.67E-04 390598.88 393601.88
I used State averge of 5 and 10 electrons with 7 active orbitals.
CASSCF energy
-931.1909549
-931.0536974
-931.0452313
-930.993597
-930.9787674