Vibrational line shapes of solvated molecules with a normal mode approach

Schvaneveldt, Stephen J.; Loring, Roger F.
February 1995
Journal of Chemical Physics;2/8/1995, Vol. 102 Issue 6, p2326
Academic Journal
We develop a theory of the vibrational absorption line shape of a solvated molecule. This approach is based on the instantaneous normal mode approximation, in which the fluid is taken to evolve on a harmonic potential surface whose curvature matches that of the true potential surface at the fluid’s initial configuration. We apply this method to the vibrational line shape of a harmonic diatomic molecule dissolved in an atomic solvent. The line shape is related to a configurationally averaged phonon Green’s function. A diagrammatic analysis of this Green’s function is shown to lead to a self-consistent approximation to the line shape. The only inputs to this calculation from other theory or simulation are the pair correlation functions for two solvent particles and for a solute atom and a solvent particle. The resulting spectra are compared with calculations for a similar model by Berne et al., based on the generalized Langevin equation [J. Chem. Phys. 93, 5084 (1990)]. © 1995 American Institute of Physics.


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