Dynamical effects on vibrational and electronic spectra of hydroperoxyl radical water clusters

Abstract

We have carried out ab initio molecular-dynamics studies on hydroperoxyl water clusters. Our studies are complemented by optimization, frequency, and excited-state calculations. The three main results we obtained are (a) the dynamically averaged energy gap between the highest-occupied molecular orbital and the lowest-unoccupied molecular orbital monotonically decreases as the number of water molecules is increased in a hydroperoxyl water cluster system, (b) the dynamical averaging of the potential-energy surface at finite temperature broadens the electronic excitation spectrum and changes the infrared spectrum in nontrivial ways, and (c) the structural analysis of our dynamics simulation indicates that the oxygen-oxygen distance in a solvated hydroperoxyl-water cluster is very similar to that found in protonated water clusters (Zundel: H5 O2+) inspite of the fact that the latter possesses a positive charge and the hydroperoxyl-water cluster does not. Dynamical charge analysis and the weak acidity of H O2 are used to justify this result. © 2005 American Institute of Physics.