Analytic ab initio-based molecular interaction potential for the BrO·H₂O complex

Authors

Ross D. Hoehn, Purdue University
Sachin D. Yeole, Purdue University
Sabre Kais, Purdue University
Joseph S. Francisco, University of Nebraska-LincolnFollow

Document Type

Article

Date of this Version

2016

Citation

THE JOURNAL OF CHEMICAL PHYSICS 144, 204121 (2016)

Comments

Published by AIP Publishing

Used by permission.

Abstract

Radical halogen oxide species play important roles within atmospheric processes, specifically those responsible for the removal of O3. To facilitate future investigations on this family of compounds, RCCSD(T)/aug-cc-pVQZ-level electronic structure calculations were employed to generate individual-molecule optimized geometries, as well as to determine the global minimum energy structure for the BrO·H₂O complex. This information facilitated the generation of several one-dimensional potential energy surface (PES) scans for the BrO·H₂O complex. Scans were performed for both the ground state and the first excited state; this inclusion is due to a low-lying first electronic excited-state energy. These rigid-geometry PES scans were used both to generate a novel analytic interaction potential by modifying the existing Thole-type model used for water and to the fitted potential function. This interaction potential features anisotropic atomic polarizabilities facilitating appropriate modeling of the physics regarding the unpaired electron residing within the p-orbitals of the oxygen atom of the bromine oxide radical. The intention of this work is to facilitate future molecular dynamics simulations involving the interaction between the BrO radical and water clusters as a first step in devising possible novel chemistries taking place at the water interface of clouds within the atmosphere.