Communication: A benchmark-quality, full-dimensional ab initio potential energy surface for Ar-HOCO

Abstract

A full-dimensional, global ab initio potential energy surface (PES) for the Ar-HOCO system is presented. The PES consists of a previous intramolecular ab initio PES for HOCO [J. Li, C. Xie, J. Ma, Y. Wang, R. Dawes, D. Xie, J. M. Bowman, and H. Guo, J. Phys. Chem. A 116, 5057 (2012)], plus a new permutationally invariant interaction potential based on fitting 12 432 UCCSD(T)-F12a/aVDZ counterpoise-corrected energies. The latter has a total rms fitting error of about 25 cm-1 for fitted interaction energies up to roughly 12 000 cm-1. Two additional fits are presented. One is a novel very compact permutational invariant representation, which contains terms only involving the Ar-atom distances. The rms fitting error for this fit is 193 cm-1. The other fit is the widely used pairwise one. The pairwise fit to the entire data set has an rms fitting error of 427 cm-1. All of these potentials are used in preliminary classical trajectory calculations of energy transfer with a focus on comparisons with the results using the benchmark potential. © 2014 AIP Publishing LLC.