The reaction of H + CH₂O: addition vs. abstraction

Abstract

The reaction of H and CH₂O, which plays an important role in combustion of hydrocarbons and alcohols, was studied in details using high-level coupled cluster calculations to construct a potential energy surface. This is followed by E,J-resolved master equation analyses to obtain rate constants as a function of both temperature and pressure. It is observed for the first time that the H-addition mechanism plays only a minor role (<10%), and can be neglected at high temperature in combustion environments. The direct H-abstraction pathway exclusively yields H₂ plus CHO. The calculated rate constants from the first principles agree reasonably well with experiments for a wide range of temperatures between 250 and 3500 K. When there are no experimental data, we provide highly accurate rate constants for kinetics modelling.

GRAPHICAL ABSTRACT

KEYWORDS:

• Coupled-cluster
• master-equation
• rate constants
• H-abstraction
• H-addition

Acknowledgments

We would like to thank Prof. John F. Stanton for his supervision, support, and helpful advices. The authors congratulate Prof. John F. Stanton on his gold age, 60th birthday, and whishes many happy returns! We wish to thank Department of Chemistry, University of Florida for the financial support. This material is based on work partly supported by the U.S. Department of Energy, Office of Basic Energy Sciences under Award DE-SC0018164.

Disclosure statement

No potential conflict of interest was reported by the author(s).

Data available statement

The authors confirm that the data supporting the findings of this study are available within the article and its supplementary materials. The (additional) data that support the findings of this study are also available on request from the corresponding author.

Additional information

Funding

This work was supported by U.S. Department of Energy: [Grant Number DE-SC0018164].