Abstract
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 language | English (US) |
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Pages (from-to) | 10909-10914 |
Number of pages | 6 |
Journal | Journal of Physical Chemistry B |
Volume | 104 |
Issue number | 46 |
DOIs | |
State | Published - Nov 23 2000 |
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry