High-accuracy first-principles-based rate coefficients for the reaction of OH and CH3OOH

Nguyen, Thanh Lam; Perera, Ajith; Peeters, Jozef

doi:10.1039/d2cp03919b

High-accuracy first-principles-based rate coefficients for the reaction of OH and CH₃OOH

Journal Article · Fri Oct 21 00:00:00 EDT 2022 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d2cp03919b· OSTI ID:2420729

^[1]; Perera, Ajith ^[2]; ^[3]

Univ. of Florida, Gainesville, FL (United States); OSTI
Univ. of Florida, Gainesville, FL (United States)
University of Leuven (Belgium)

Here, the ˙OH-initiated oxidation of methyl hydroperoxide, which plays an important role in the atmospheric chemistry of methane, was theoretically characterized using high-accuracy composite amHEAT-345(Q) coupled-cluster calculations followed by a two-dimensional E,J resolved master equation analysis. The reaction is found to proceed through two distinct hydrogen-bonded pre-reactive complexes leading to two product channels, in accord with the experimental observations: (i) ˙OH + CH₃OOH → CH₃OO˙ + H₂O with a yield of 0.8 ± 0.1, and (ii) ˙OH + CH₃OOH → HCHO + ˙OH + H₂O with a yield of 0.2 ± 0.1. The calculated reaction enthalpies are within 0.2 kcal mol^-1 of the benchmark ATcT values. Overall thermal rate coefficients obtained from first principles are found to be in the low-pressure limit at atmospheric pressure; the total rate coefficient can be expressed over the T = 200–450 K range as k(T) = 5.0 × 10^-12 × T^-0.152 × exp(287/T) cm³ s^-1, strongly supporting the experimental results of Vaghjiani and Ravishankara, with which this expression agrees within ca. 15%. The current results show that (i) is the principal reaction channel and support the view that, due to its inherently fast transformations, CH₃OOH is an important redistribution species for HO_x˙ radicals in the Earth's atmosphere.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Florida, Gainesville, FL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018164

OSTI ID:: 2420729

Alternate ID(s):: OSTI ID: 1894962

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 43 Vol. 24; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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