The association/dissociation reaction path for ozone (O2 + O ↔ O3) is notoriously difficult to describe accurately using ab initio electronic structure theory, due to the importance of both strong and dynamic electron correlations. Experimentally, spectroscopic studies of the highest lying recorded vibrational states combined with the observed negative temperature dependence of the kinetics of oxygen isotope exchange reactions confirm that the reaction is barrierless, consistent with the latest potential energy surfaces. Previously reported potentials based on Davidson-corrected internally contracted multireference configuration interaction (MRCI) suffer from a spurious reef feature in the entrance channel even when extrapolated towards the complete basis set limit. Here, we report an analysis of comparisons between a variety of electronic structure methods including internally contracted and uncontracted MRCI (with and without Davidson corrections), as well as full configuration interaction quantum Monte Carlo, fixed-node diffusion Monte Carlo, and density matrix renormalization group.



Research Center/Lab(s)

Center for High Performance Computing Research

Keywords and Phrases

Association Reactions; Electronic Structure; Ozone; Potential Energy; Quantum Chemistry; Reaction Kinetics; Spectroscopic Analysis; Statistical Mechanics; Temperature Distribution, Complete Basis Set Limit; Density Matrix Renormalization Group; Electronic Structure Theory; Fixed Node Diffusion Monte Carlo; Full Configuration Interaction; Multi Reference Configuration Interactions; Oxygen Isotope Exchange; Spectroscopic Studies, Monte Carlo Methods

International Standard Serial Number (ISSN)

0021-9606; 1089-7690

Document Type

Article - Journal

Document Version

Final Version

File Type





© 2017 The Authors, All rights reserved.

Publication Date

01 Oct 2017

Included in

Chemistry Commons