Kinetics of the Hydrogen Abstraction PAH + •OH → PAH Radical + H2O Reaction Class: An Application of the Reaction Class Transition State Theory (RC-TST) and Structure-Activity Relationship (SAR)

Maciej Baradyn; Artur Ratkiewicz

doi:10.1021/acs.jpca.8b10988

Kinetics of the Hydrogen Abstraction PAH + ^•OH → PAH Radical + H₂O Reaction Class: An Application of the Reaction Class Transition State Theory (RC-TST) and Structure-Activity Relationship (SAR)

J Phys Chem A. 2019 Jan 31;123(4):750-763. doi: 10.1021/acs.jpca.8b10988. Epub 2019 Jan 15.

Authors

Maciej Baradyn¹, Artur Ratkiewicz¹

Affiliation

¹ Institute of Chemistry , University of Bialystok , ul. Ciolkowskiego 1K 15-245 Bialystok , Poland.

PMID: 30596495
DOI: 10.1021/acs.jpca.8b10988

Abstract

A reaction class transition state theory (RC-TST) augmented with structure-activity relationship (SAR) methodology is applied to predict high-pressure limit thermal rate constants for hydrogen abstraction by ^•OH radical from polycyclic aromatic hydrocarbons (PAHs) reaction class in the temperature range of 300-3000 K. The rate constants for the reference reaction of C₆H₆ + ^•OH → C₆H₅ + H₂O is calculated by the canonical variational transition state theory (CVT) with small curvature tunneling (SCT). Only the reaction energy is needed to predict RC-TST rates for other processes within the family, the parameters needed were obtained from M06-2X/cc-pVTZ data for a training set of 34 reactions. The systematic error of the resulting RC-TST rates is smaller than 50% in comparison with explicit rate calculations, which facilitates application of the proposed methodology to the automated reaction mechanism generators (ARMGs) schemes.