Structures, Energetics, and Vibrational Spectra of H2O2××× (H2O)n, n = 1—6 Clusters: Ab initio Quantum Chemical Investigations.

Abstract

Hydrogen-bonded heteroclusters of H2O2···(H2O)n, with n varying from 1 through 6, have been investigated herein employing ab initio quantum chemical methods. For a given n, several energetically comparable conformers emerge as local minima on the potential energy surface (PES). All of the conformers obtained at restricted Hartree−Fock (RHF) and Moller−Plesset second-order perturbation (MP2) levels of theory exhibit parallel trends in energy hierarchy. The effect of clustering by water on the modification in the vibrational frequencies has also been investigated and further, a many-body interaction-energy analysis is carried out providing insights into cooperativity in H2O2···(H2O)n clusters.