System–bath relaxation theory approach to nonadiabatic coupling effects on condensed phase electronic absorption spectra
Evans, D. G. ; Coalson, R. D.
College Park, Md. : American Institute of Physics (AIP)
Published 1994
College Park, Md. : American Institute of Physics (AIP)
Published 1994
| ISSN: |
1089-7690
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|---|---|
| Source: |
AIP Digital Archive
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| Topics: |
Physics
Chemistry and Pharmacology
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| Notes: |
Separation of a many-body system into a primary system plus a bath of background modes enables approximate calculation of electronic absorption spectra and zero-temperature resonance Raman scattering cross sections in cases where there is nonadiabatic coupling between two or more Born–Oppenheimer excited-state potential surfaces. In particular, the low-resolution optical line shape theory recently developed to describe curve-crossing phenomena [D. G. Evans and R. D. Coalson, J. Chem. Phys. 99, 6264 (1993)] is extended to systems where there is a primary nuclear coordinate mode that is characterized by large excited-state displacements and an ensemble of weakly displaced bath modes. The accuracy of the resulting approximation scheme is illustrated using the spectroscopic spin-boson model, in which all surfaces are harmonic, and path integral techniques can be used to obtain exact results. Application to more complicated systems is discussed.
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| Type of Medium: |
Electronic Resource
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| URL: |