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

作者：Hoehn Ross D; Yeole Sachin D; Kais Sabre; Francisco Joseph S^*

来源：Journal of Chemical Physics, 2016, 144(20): 204121.

DOI：10.1063/1.4950956

Radical halogen oxide species play important roles within atmospheric processes, specifically those responsible for the removal of O-3. 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 center dot H2O complex. This information facilitated the generation of several one-dimensional potential energy surface (PES) scans for the BrO center dot 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. Published by AIP Publishing.

• 出版日期2016-5-28