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.