Theoretical Kinetics studies of isoprene peroxy radical chemistry: The fate of Z-δ-(4-OH, 1-OO)-ISOPOO radical

Yan Li; Rui Ming Zhang; Xuefei Xu

doi:10.1016/j.ecoenv.2023.115553

Theoretical Kinetics studies of isoprene peroxy radical chemistry: The fate of Z-δ-(4-OH, 1-OO)-ISOPOO radical

Ecotoxicol Environ Saf. 2023 Nov 1:266:115553. doi: 10.1016/j.ecoenv.2023.115553. Epub 2023 Oct 13.

Authors

Yan Li¹, Rui Ming Zhang¹, Xuefei Xu²

Affiliations

¹ Center for Combustion Energy, Department of Energy and Power Engineering, and Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China.
² Center for Combustion Energy, Department of Energy and Power Engineering, and Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China. Electronic address: xuxuefei@tsinghua.edu.cn.

PMID: 37839188
DOI: 10.1016/j.ecoenv.2023.115553

Abstract

The OH radical recycling mechanism in isoprene oxidation is one of the most exciting topics in atmospheric chemistry, and the corresponding studies expand our understanding of oxidation mechanisms of volatile organic compounds in the troposphere and provide reliable evidence to improve and develop conventional atmospheric models. In this work, we performed a detailed theoretical kinetics study on the Z-δ-(4-OH, 1-OO)-ISOPOO radical chemistry, which is proposed as the heart of OH recycling in isoprene oxidation. With the full consideration of its accumulation and consumption channels, we studied and discussed the fate of Z-δ-(4-OH, 1-OO)-ISOPOO radical by solving the energy-resolved master equation over a broad range of conditions, including not only room temperatures but also high temperatures of a forest fire or low temperatures and pressures of the upper troposphere. We found non-negligible pressure dependence of its fate at combustion temperatures (up to two orders of magnitude) and demonstrated the significance of both the multi-structural torsional anharmonicity and tunneling for accurately calculating kinetics of the studied system. More interestingly, the tunneling effect on the phenomenological rate constants of the H-shift reaction channel is also found to be pressure-dependent due to the competition with the O₂ loss reaction. In addition, our time evolution calculations revealed a two-stage behavior of critical species in this reaction system and estimated the shortest half-lives for the Z-δ-(4-OH, 1-OO)-ISOPOO radical at various temperatures, pressures and altitudes. This detailed kinetics study of Z-δ-(4-OH, 1-OO)-ISOPOO radical chemistry offers a typical example to deeply understand the core mechanism of OH recycling pathways in isoprene oxidation, and provides valuable insights for promoting the development of relevant atmospheric models.

Keywords: H-shift Reaction; Kinetics; Peroxy Radical; Pressuredependence; Transition state theory.

MeSH terms

Butadienes
Hydroxyl Radical* / chemistry
Kinetics
Models, Theoretical*
Temperature

Substances

isoprene
Hydroxyl Radical
Butadienes