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Following excited states in a 1D-scan.

Pedro Silva
pedros@ufp.pt

I am interested in following the energies of several excited states as a specific bond is lenghtened. I have several optimized geometries along this PES, and I have computed the excited states through TDDFT.
In order to check whether the excited states cross, I have analyzed the EXCITATIONS/DEEXCITATIONS part of the output. In contiguous points of the surface, I find a strange discrepancy in this section:

Geometry A:


         ----------------------------------------------
         EXCITATIONS & DEEXCITATIONS     SAP COEFFICENT
         FROM MO     TO MO
         ----------------------------------------------
         
          223        229                  -0.26224016
         
          224        230                   0.78233561
         
          228        231                   0.40256033

         ----------------------------------------------


Geometry B:


         ----------------------------------------------
         EXCITATIONS & DEEXCITATIONS     SAP COEFFICENT
         FROM MO     TO MO
         ----------------------------------------------

          223        229                   0.16069884
         
          224        230                  -0.71201471
         
          228        231                  -0.53043190

         ----------------------------------------------

As you can see from this truncated output, the involved orbitals seem to be the same (the absolute values of the SAP have not changed much) but the signs of the SAP coefficients have flipped, so that they now are deexcitations instead of excitations...  So my doubt is : are these the same excited state?

Thanks for any help

Pedro

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