Hydrogen Abstraction Reactions from Phenolic Compounds by Peroxyl Radicals: Multireference Character and Density Functional Theory Rate Constants

Galano Annia; Munoz-Rugeles Leonardo; Raul Alvarez-Idaboy Juan; Bao Junwei Lucas; Truhlar Donald G.

首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Hydrogen Abstraction Reactions from Phenolic Compounds by Peroxyl Radicals: Multireference Character and Density Functional Theory Rate Constants

【24h】

Hydrogen Abstraction Reactions from Phenolic Compounds by Peroxyl Radicals: Multireference Character and Density Functional Theory Rate Constants

机译：过氧自由基从酚类化合物中提取氢的反应：多参考特征和密度泛函理论速率常数

获取原文

获取原文并翻译 | 示例

掌桥外文数据库（机构版） >>

开具论文收录证明 >>

文献代查 >>

页面导航

摘要
著录项
相似文献
相关主题

摘要

An assessment of multireference character in transition states is considered to be an important component in establishing the expected reliability of various electronic structure methods. In the present work, the multireference characters of the transition states and the forming and breaking of bonds for a large set of hydrogen abstraction reactions from phenolic compounds by peroxyl radicals have been analyzed using the T-1, M, B-1, and GB(1) diagnostics. The extent of multireference character depends on the system and on the conditions under which the reaction takes place, and some systematic trends are observed. In particular, the multireference character is found to be reduced by solvation, the size of the phenolic compound, and deprotonation in aqueous solution. However, the deviations of calculated rate constants from experimental ones are not correlated with the extent of multireference character. The performance of single-determinant density functional theory was investigated for the kinetics of these reactions by comparing calculated rate constants to experimental data; the results from these analyses showed that the M05 functional performs well for the task at hand.

机译：评估过渡态下的多参考特性是建立各种电子结构方法的预期可靠性的重要组成部分。在目前的工作中，已使用T-1，M，B-1和GB分析了过氧自由基从大量酚类化合物中夺取大量氢的过渡态以及键的形成和断裂的多参考特征。（1）诊断。多参考特征的程度取决于系统和反应发生的条件，并且观察到一些系统趋势。特别地，发现通过溶剂化，酚类化合物的尺寸和水溶液中的去质子化降低了多参考特性。但是，计算出的速率常数与实验值的偏差与多参考特征的程度无关。通过将计算的速率常数与实验数据进行比较，研究了单决定密度泛函理论对这些反应动力学的影响。这些分析的结果表明，M05功能可以很好地完成当前的任务。

著录项

来源
《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2016年第27期|共9页
作者
Galano Annia; Munoz-Rugeles Leonardo; Raul Alvarez-Idaboy Juan; Bao Junwei Lucas; Truhlar Donald G.;
展开▼
作者单位

展开▼
收录信息
原文格式 PDF
正文语种 eng
中图分类
关键词

相似文献

外文文献
中文文献
专利

1. Hydrogen Abstraction Reactions from Phenolic Compounds by Peroxyl Radicals: Multireference Character and Density Functional Theory Rate Constants [J] . Galano Annia, Munoz-Rugeles Leonardo, Raul Alvarez-Idaboy Juan, The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2016,第27期

机译：过氧自由基从酚类化合物中提取氢的反应：多参考特征和密度泛函理论速率常数
2. Density functional theory thermal rate constant calculation of hydrogen abstraction reactions of trans-cyc-CF2CF2CF2CHFCHF and cyc-CF2CF2CF2CHFCH2 with OH radicals [J] . Hashemi S. Rasoul, Zokaie Meymanat, Saheb Vahid, Journal of Fluorine Chemistry . 2020,第1期

机译：密度函数理论热速率恒定计算Trans-Cyc-CF2CF2CF2CHFCHF和CYC-CF2CF2CF2CHFCH2与OH自由基的氢气抽象反应
3. High-level ab initio and density functional theory study on reaction path and rate constant of the hydrogen abstraction reaction SiH_2Cl_2 + H -> SiHCl_2 + H_2 [J] . Xin Yu, Shen-Min Li, Zhen-Feng Xu, Journal of Molecular Structure. Theochem: Applications of Theoretical Chemistry to Organic, Inorganic and Biological Problems . 2001,第1a3期

机译：析氢反应SiH_2Cl_2 + H-> SiHCl_2 + H_2的反应路径和速率常数的从头算和密度泛函理论研究
4. Hydrogen Abstraction Reaction of Hydrofluorocarbons by the Hydroxyl Radical. a Hybrid Density Functional Theory with Specific Reaction Parameter Study [C] . Saravanan Swaminathan, Sean Mikel, Donald P. Visco Jr. International Symposium on Runaway Reactions, Pressure Relief Design and Effluent Handling American Institute of Chemical Engineers/American Chemical Society Management Conference . 2005

机译：氢氟烃对羟基的氢气抽取反应。具有特定反应参数研究的混合密度功能理论
5. I. Experimental studies of gamma-intramolecular hydrogen abstraction in alkylperoxy radicals and decomposition of the resulting 1,3-hydroperoxyalkyl radicals. II. Dynamic effects in moderately exothermic reactions [D] . Cohen, Elizabeth Susan. 1998

机译：I.在烷基过氧自由基中γ-分子内氢的夺取和所得1，3-氢过氧烷基自由基分解的实验研究。二。中度放热反应的动态影响
6. Theoretical derivation for reaction rate constants of H abstraction fromthiophenol by the H/O radical pool [O] . Marwan Batiha, Mohammednoor Altarawneh, Mohammad Al-Harahsheh, -1

机译：从中提取H的反应速率常数的理论推导H / O自由基池中的苯酚
7. Rate constants for hydrogen abstraction reactions by the hydroperoxyl radical from methanol, ethenol, acetaldehyde, toluene, and phenol [O] . Altarawneh, Mohammednoor, Al-Muhtaseb, Ala'a H., Dlugogorski, Bogdan Z., 2011

机译：氢过氧自由基从甲醇，乙醇，乙醛，甲苯和苯酚进行氢提取反应的速率常数

Hydrogen Abstraction Reactions from Phenolic Compounds by Peroxyl Radicals: Multireference Character and Density Functional Theory Rate Constants

摘要

著录项

相似文献

相关主题

期刊订阅