Baradyn Maciej, Ratkiewicz Artur
Institute of Chemistry , University of Bialystok , ul. Ciolkowskiego 1K 15-245 Bialystok , Poland.
J Phys Chem A. 2019 Jan 31;123(4):750-763. doi: 10.1021/acs.jpca.8b10988. Epub 2019 Jan 15.
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 CH + OH → CH + HO 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.
一种结合了构效关系（SAR）方法的反应类过渡态理论（RC-TST）被用于预测在300-3000K温度范围内，OH自由基从多环芳烃（PAHs）反应类中夺取氢的高压极限热速率常数。CH + OH → CH + HO的参考反应速率常数通过具有小曲率隧道效应（SCT）的正则变分过渡态理论（CVT）计算得出。预测该反应族内其他过程的RC-TST速率仅需反应能量，所需参数从34个反应的训练集的M06-2X/cc-pVTZ数据中获得。与显式速率计算相比，所得RC-TST速率的系统误差小于50%，这有利于将所提出的方法应用于自动反应机理生成器（ARMGs）方案。
