Anharmonic Assignment of the Water Octamer Spectrum in the OH Stretch Region.

Abstract

We interface the quasi-classical trajectory approach with an ab initio potential energy surface for water to assign the vibrational spectroscopical features of the OH stretch region of the water octamer cluster, which is considered to be a precursor of ice. An attempt by Li et al. to assign their recent reference experiment involved lower-level calculations based on an ad hoc scaled harmonic approach. Differently from the conclusions of this previous assignment, which invoked the contribution of 5 conformers and a solvated form of the water heptamer in the spectrum, we find out that the spectroscopic features can be related to the 4 conformers of the octamer lying lower in energy.