PNNL

Abstract

In recent years, the ClO free radical has been found to play an important role in the ozone removal processes in the atmosphere. In this work, we present a Potential Energy Surface (PES) Scan of the ClO•H2O system with high-level ab initio methods. Because of the existence of low-lying excited states of the ClO•H2O complex, and their potential impact on the chemical behavior of the ClO radical in the atmosphere, we perform a PES scan at CCSD(T)/aug-cc-pVTZ level of both the first excited and ground states in order to model the physics of the unpaired electron in the ClO radical. Analytical potentials for both ground and excited states, with internal molecular coordinates held fixed, were built based on a Thole Type Model. The two minima of the ClO•H2O complex are recovered by the analytical potential. This work was supported by the Office of Basic Energy Sciences of the Department of Energy, in part by the Chemical Sciences program and in part by the Engineering and Geosciences Division. The Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.