Raman Excitation Profiles with Self-Consistent Excited-State Displacements

Autor: Zoltán G. Soos, Andrew Bruce Bocarsly, M. H. Hennessy, and D. F. Watson
Rok vydání: 2000
Předmět:
Zdroj: The Journal of Physical Chemistry B. 104:10909-10914
ISSN: 1520-5207
1520-6106
DOI: 10.1021/jp0011084
Popis: Raman excitation profiles (REPs) are computed in the time domain for harmonic modes with excited-state displacement g and measured at multiple excitation frequencies ωL in a bimetallic complex with a metal-to-metal charge-transfer band and 10 coupled modes. Self-consistency is required because the time evolution depends on all displaced modes rather than the individual intensities used in the short-time approximation for g(0). Self-consistency ensures that g is independent of ωL for a single resonance. Exact REPs for displaced oscillators show the importance of vibronic lifetimes and marked deviations from the short-time approximation at molecular frequencies. Spectra at multiple ωL indicate scattering from another electronic excitation with displacement h that is also found self-consistently. Mode-specific Raman data at multiple ωL require additional parameters to yield reliable structural information. Harmonic oscillators with self-consistent displacements are a first approximation to systems with many ...
Databáze: OpenAIRE