Electronic Structure via Simulated Annealing Techniques: Solvent Shifts of Guest Atom Transition Frequencies in Rare Gas Clusters

Author Institution: Department of Chemistry, Ohio State UniversityThe spectroscopic shifts of guest species in rare gas clusters are studied as a model for solvation in condensed phases, and as a probe of the cluster structure. These clusters are thought to exist in both fluid and solid-like forms, depending upon experimental conditions, and the observation of several spectroscopic peaks has been interpreted as arising from several distinct cluster isomers. We report preliminary results of a simulated annealing calculation for guest atoms in argon clusters. Cluster configurations are sampled by standard molecular dynamics simulation of the nuclear coordinates. Quenches at regular intervals identify locally stable cluster arrangements. Use of simulated annealing techniques permits calculation of the Born-Oppenheimer surface for nuclear motion and transition frequencies in configurations of low symmetry