Raman excitation profiles with self-consistent excited-state displacements

M. H. Hennessy, Z. G. Soos, D. F. Watson, Andrew Bruce Bocarsly

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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-tometal 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 coupled modes.

Original languageEnglish (US)
Pages (from-to)10909-10914
Number of pages6
JournalJournal of Physical Chemistry B
Issue number46
StatePublished - Nov 23 2000

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry


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