Franck--Condon profiles in photodetachment-photoelectron spectra of HS$_2^-$ and DS$_2^-$ based on vibrational configuration interaction wavefunctions

Joonsuk Huh (1) , Michael Neff (2) , Guntram Rauhut (3) , Robert Berger (4)

1 Frankfurt Institute for Advanced Studies
2 Institute of Theoretical Chemistry
3 Institute of Theoretical Chemistry
4 FIAS - Frankfurt Institute for Advanced Studies

Explicitly electron correlating coupled cluster calculations, CCSD(T)-F12a, were performed to determine three-dimensional potential energy hypersurfaces of disulfanide and disulfanyl in an automated approach. Surfaces for different electronic states were used in a Watson rovibrational Hamiltonian ansatz to obtain the correlated anharmonic vibrational wavefunctions. Subsequently the anharmonic Franck--Condon overlap integrals were evaluated. The computed Franck--Condon profiles were compared to experimental photodetachment-photoelectron spectra and confirm essentially the assignments made previously. The profiles indicate, however, additional weaker, and as of yet unresolved, additional features.

Mots clés: Physical Sciences

Joonsuk Huh, Michael Neff, Guntram Rauhut, Robert Berger. Franck--Condon profiles in photodetachment-photoelectron spectra of HS$_2^-$ and DS$_2^-$ based on vibrational configuration interaction wavefunctions. Molecular Physics, 2010, 108 (03-04), pp.409-423. ⟨10.1080/00268970903521178⟩. ⟨hal-00580674⟩