Quantum Monte Carlo Investigation of the H-transfer Reaction of Criegee Intermediate CH3CHOO: A Benchmark Calculation

TL;DR

This study uses fixed-node diffusion Monte Carlo to accurately determine the barrier height and reaction energy of the H-transfer in Criegee intermediate CH3CHOO, validating the method against experimental data and other computational approaches.

Contribution

It provides benchmark FN DMC calculations for the H-transfer reaction of CH3CHOO, demonstrating its reliability and comparing various computational methods against experimental results.

Findings

FN DMC barrier height: 16.60 kcal/mol, agrees with experiment

CCSD(t) barrier heights closely match FN DMC

MP2 significantly underestimates the barrier height

Abstract

We perform the fixed-node diffuse Monte Carlo (FN DMC) calculations to determine the barrier height and reaction energy of a critical reaction, the H-transfer reaction from syn-CH3CHOO to vinyl hydroperoxide. The FN DMC barrier height is found to be 16.60+/-0.35 kcal/mol which agrees well with the experimental measurement within a few tenths of kcal, justifying the reliability of the FN DMC method for predicting barrier height of the rapid unimolecular reaction of Criegee intermediates. By comparing the predictions from the CCSD(t), G3 (MCG3), DFT and MP2 methods with respect to the FN DMC results and available experiment measurement, we found that the CCSD(t) barrier heights agree with the FN DMC counterpart within statistical errors, and is within a closer agreement with experiment and FN DMC prediction than the G3(MCG3) models. Barrier heights predicted from the relatively more economic DFT methods are within a few tenths kcal of the FN DMC prediction. MP2 method severely underestimates the barrier height. FN DMC prediction for the reaction energy is -17.25+/-0.31 kcal/mol, setting an upper limit for the reaction energies predicted by the post Hartree-Fock methods and a lower limit for the DFT reaction energies. We provide FN DMC input for clarifying the energetic uncertainties in the critical H-transfer reaction of syn-CH3CHOO. The quantitatively close agreements between the FN DMC barrier height and experimental measurement, and between the predictions from the FN DMC and G3 model for the reaction energy provide a theoretical basis for resolving the energy uncertainty in this reaction.