Umbrella sampling of solute vibrational line shifts in mixed quantum-classical molecular dynamics simulations.
An umbrella sampling approach for vibrational frequency line shifts is presented. The technique allows for efficient sampling of the solvent configurations corresponding to frequency shifts of a solute in mixed quantum-classical simulations. The approach is generally applicable and can also be used within traditional perturbation theory calculations of frequency shifts. It is particularly useful in the extraction of detailed mechanistic information about the solute-solvent interactions giving rise to the frequency shifts. The method is illustrated by application to the simple I2 in a liquid Xe system, and the advantages are discussed.
Morales
Christine M
CM
Department of Chemistry, University of Kansas, Lawrence, Kansas 66045, USA.
Thompson
Ward H
WH