Theoretical kinetic study of thermal unimolecular decomposition of cyclic alkyl radicals

TL;DR

This paper presents a theoretical quantum chemical study of the unimolecular decomposition of cyclic alkyl radicals, providing detailed energy barriers, rate constants, and thermochemical data to enhance understanding of cyclic hydrocarbon reactions.

Contribution

It offers the first systematic quantum chemical analysis of cyclic alkyl radical decomposition, including energy barriers and rate constants at the CBS-QB3 level.

Findings

Calculated energy barriers and rate constants for cyclic alkyl radical decomposition.

Provided thermochemical data from isodesmic reactions.

Included effects of hindered rotors in thermochemical calculations.

Abstract

While many studies have been reported on the reactions of aliphatic hydrocarbons, the chemistry of cyclic hydrocarbons has not been explored extensively. In the present work, a theoretical study of the gas-phase unimolecular decomposition of cyclic alkyl radicals was performed by means of quantum chemical calculations at the CBS-QB3 level of theory. Energy barrier and high-pressure limit rate constants were calculated systematically. Thermochemical data were obtained from isodesmic reactions and the contribution of hindered rotors was taken into account. Classical transition state ...