Vibronic structure of the valence π-photoelectron bands in furan, pyrrole, and thiophene

Journal of Chemical Physics

Volumn 109, Issue 3, 1998, Pages 1025-1040

  Trofimov, A B ^a   Koppel H ^a   Schirmer, J ^a  

^a UNIVERSITY OF HEIDELBERG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 22244452362     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.476645     Document Type: Article

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54. The observed overall shift of the theoretical spectrum with respect to the experimental one results from an error in the calculated vertical ionization energies (Sec. IIIC). This kind of disagreement is disregarded in the present paper as the absolute energy values are only of a minor importance for our study of vibrational excitations. For the same reason the overall shift acquired by the spectra computed in different approximations is also not discussed in the following. The compared spectral envelopes are aligned everywhere so as to ensure their maximal coincidence.
55. The theoretical approach of Takeshita et al. (Refs. 9 10 11) is based on the separate description of the initial and final electronic states. It, therefore, accounts for the changes in the normal coordinates and vibrational frequencies due to ionization. In the case of simple Poisson intensity distributions the final-state vibrational frequencies are assumed to be the same as in the electronic ground state.
56. Because our calculations are performed in the diabatic basis where the final states are described by Eqs. (2.1) and (2.6), the interpretation of the results represents a difficult task. Even when the actual physical situation is simple (e.g., when the adiabatic approximation holds) we have to resort to additional considerations to aid the assignment. A rigorous theoretical approach would be to transform the results to the adiabatic basis which is, however, not feasible for computational reasons.
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