title: Theoretical investigation of the electronically excited states of chlorine hydrate.
abstract: As a step toward a first principles characterization of the optical properties of chlorine hydrate, we have calculated the electronic absorption spectrum of a chlorine molecule trapped in dodecahedral (H2O)20 and hexakaidodecahedral (H2O)24 cages. For comparison, spectra were also calculated for an isolated Cl2 molecule as well as for selected Cl2(H2O)n, n < or =8, clusters cut out of the Cl2(H2O)20 cluster, allowing us to follow the evolution of the low-lying excited states with increasing number of surrounding water molecules. Although encapsulation of a chlorine molecule within the water cages has relatively little effect on its low-lying valence transitions, it does result in a large number of solvent-to-solute charge-transfer transitions at energies starting near 48,000 cm(-1).
authors.affiliation: Department of Chemistry and Center for Molecular and Materials Simulations, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
authors.forename: Daniel P
authors.initials: DP
authors.lastname: Schofield
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Jordan