title: Electronic absorption line shapes at the water liquid/vapor interface.
abstract: In order to investigate the factors that contribute to the electronic absorption line shape of a chromophore adsorbed at the water liquid/vapor interface, molecular dynamics simulations of a series of dipolar solutes undergoing various electronic transitions at various locations along the interface normal are studied. For electronic transitions that involve a change in the permanent dipole moment of the solute, the transition from the bulk water to the liquid/vapor interface involves a spectral shift consistent with the lower polarity of the interface. The change in the spectral width relative to that in the bulk is determined by several factors, which, depending on the nature of the transition and the dipole moment of the initial state, can result in a narrowing or broadening of the spectrum. These factors include the location of the interface region (which directly correlates with local polarity), the heterogeneity of the local solvation shell, and the width of the surface region. The contribution of the heterogeneity of the local solvation shell can be determined by comparing surface water with bulk methanol, whose polarity is comparable to one of the surface regions.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Santa Cruz, California 95064, USA.
authors.forename: Katherine V
authors.initials: KV
authors.lastname: Nelson
authors.forename: Ilan
authors.initials: I
authors.lastname: Benjamin