Electronic spectra in bulk water and at the water liquid/vapor interface. Effect of solvent and solute polarizabilities

The role of solvent and solute many-body polarizabilities in influencing the electronic absorption line shapes for a model dipolar solute at the water liquid/vapor interface is investigated using molecular dynamics computer simulations. Several choices for the charge distribution in the solute excited state and for the solute atomic polarizability are considered. A comparison is made between the results using both polarizable and non-polarizable water models. Solvent polarizability is found to have a more substantial effect on the peak absorption spectrum than solute polarizability, especially for transitions to more polar excited states, and somewhat less so at the interface than in the bulk. (C) 1998 Elsevier Science B.V. All rights reserved.