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Re^5: absorption/emission MCSCF (again)

sanya
sanya@photonics.ru


Dear Jonas,

After "LAGRANGIAN CONVERGED" line you'll find " -MCCI- BASED ON OPTIMIZED ORBITALS". There are fields like "STATE #    1  ENERGY =..." and "CSF      COEF    OCCUPANCY". That is, the energies of the CASSCF states and their configuration composition (occupancy schemes and weights). Thus, the following lines after STATE #1 energy

     CSF      COEF    OCCUPANCY (IGNORING CORE)
     ---      ----    --------- --------- -----
      19   -0.308659  2222020000
      21    0.876990  2222200000

mean that CSF with occupancy 2222020000 enters State #1 with the coef. -0.308659, and CSF with occupancy 2222200000 enters State #1 with the coef. 0.876990. That is, State #1 is dominated by 2222200000 CSF, but the weight of doubly excited CSF 2222020000 is not small.

Additionally, you may look at the natural and optimized orbitals (say, by ChemCraft) to see which orbitals are involved in the transitions.

For absorption spectrum, do XMCQDPT at the optimized S0 geometry with the corresponding CASSCF orbitals. You'll get both energies and transition moments, which can be readily converted to oscillator strengths. For fluorescence spectrum, optimize S1 state by CASSCF and do XMCQDPT at the optimized S1 geometry with the corresponding CASSCF orbitals.

On Sat Sep 24 '11 11:17pm, Jonas Baltrusaitis wrote
---------------------------------------------------
>Sanya,

>I guess I am not sure what information I can extract from MCSCF output. I got [6,7] calculation to converge of 5 states with averaging, but that's pretty much it: no excited state energies (I know it can't do oscillator strengths) as I am used to, e.g. no roots, no spectrum.

>It just gave me converged energy

> ITER    TOTAL ENERGY          DEL(E)    LAG.ASYMM.  SQCDF  MICIT   DAMP
>   1   -1750.901486383   -1750.901486383  0.000000 2.684E-07  5   0.0000
>     ----------START APPROXIMATE SECOND ORDER MCSCF----------
>   2   -1750.901486383       0.000000000  0.000000 9.671E-11  1   0.0000
>   3   -1750.901486383       0.000000000  0.000000 8.462E-11  1   0.0000
>   4   -1750.901486384       0.000000000  0.000000 3.346E-11  1   0.0000
>   5   -1750.901486384       0.000000000  0.000000 4.112E-11  1   0.0000

>          --------------------
>          LAGRANGIAN CONVERGED
>          --------------------

> FINAL MCSCF ENERGY IS    -1750.9014863835 AFTER   5 ITERATIONS
> .....DONE WITH MCSCF ITERATIONS.....
>
>
>I will do XMCQDPT, will that give me absorption spectrum? Or I should use MCSCF to calculated excited state optimizaton followed by XMCQDPT for the spectrum?

>Jonas


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