Thermal Rate Coefficients and Kinetic Isotope Effects for the Reaction OH + CH4 → H2O + CH3 on an ab Initio-Based Potential Energy Surface

被引：17

作者：

Li, Jun ^{[1
]}

Guo, Hua ^{[2
]}

机构：

[1] Chongqing Univ, Sch Chem & Chem Engn, Chongqing 401331, Peoples R China

[2] Univ New Mexico, Dept Chem & Chem Biol, Albuquerque, NM 87131 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2018年 / 122卷 / 10期

基金：

中国国家自然科学基金;

关键词：

TRANSITION-STATE THEORY; QUANTUM SCATTERING CALCULATIONS; POTENTIAL-ENERGY SURFACES; RATE CONSTANTS; AB-INITIO; RADICAL REACTIONS; REACTION DYNAMICS; FLASH-PHOTOLYSIS; SHOCK-TUBE; METHANE;

D O I：

10.1021/acs.jpca.8b01201

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Thermal rate coefficients for the title reaction and its various isotopologues are computed using a tunneling-corrected transition-state theory on a global potential energy surface recently developed by fitting a large number of high-level ab initio points. The calculated rate coefficients are found to agree well with the measured ones in a wide temperature range, validating the accuracy of the potential energy surface. Strong non-Arrhenius effects are found at low temperatures. In addition, the calculations reproduced the primary and secondary kinetic isotope effects. These results confirm the strong influence of tunneling to this heavy-light-heavy hydrogen abstraction reaction.

引用

页码：2645 / 2652

页数：8

共 70 条

[1] Communication: Full dimensional quantum rate coefficients and kinetic isotope effects from ring polymer molecular dynamics for a seven-atom reaction OH + CH4 → CH3 + H2O
Allen, Joshua W.
Green, William H.
Li, Yongle
Guo, Hua
Suleimanov, Yury V.
[J]. JOURNAL OF CHEMICAL PHYSICS, 2013, 138 (22)
[2] Kinetics of OH radical reactions with methane in the temperature range 295-660 K and with dimethyl ether and methyl-tert-butyl ether in the temperature range 295-618 K
Bonard, A
Daële, V
Delfau, JL
Vovelle, C
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (17) : 4384 - 4389
[3] Temperature-dependent kinetics of the gas-phase reactions of OH with Cl2, CH4, and C3H8
Bryukov, MG
Knyazev, VD
Lomnicki, SM
McFerrin, CA
Dellinger, B
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (47) : 10464 - 10472
[4] CARBON KINETIC ISOTOPE EFFECT IN THE OXIDATION OF METHANE BY THE HYDROXYL RADICAL
CANTRELL, CA
SHETTER, RE
MCDANIEL, AH
CALVERT, JG
DAVIDSON, JA
LOWE, DC
TYLER, SC
CICERONE, RJ
GREENBERG, JP
[J]. JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 1990, 95 (D13) : 22455 - 22462
[5] Statistical thermodynamics of bond torsional modes
Chuang, YY
Truhlar, DG
[J]. JOURNAL OF CHEMICAL PHYSICS, 2000, 112 (03) : 1221 - 1228
[6] Single- and multireference electronic structure calculations for constructing potential energy surfaces
Dawes, Richard
Ndengue, Steve A.
[J]. INTERNATIONAL REVIEWS IN PHYSICAL CHEMISTRY, 2016, 35 (03) : 441 - 478
[7] ABINITIO PREDICTION OF THE BARRIER HEIGHT FOR ABSTRACTION OF H FROM CH4 BY OH
DOBBS, KD
DIXON, DA
KOMORNICKI, A
[J]. JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (11) : 8852 - 8858
[8] A KINETIC-STUDY OF OH RADICAL REACTIONS WITH METHANE AND PERDEUTERATED METHANE
DUNLOP, JR
TULLY, FP
[J]. JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (43) : 11148 - 11150
[9] Multicoefficient gaussian-3 calculation of the rate constant for the OH+CH4 reaction and its 12C/13C kinetic isotope effect with emphasis on the effects of coordinate system and torsional treatment
Ellingson, Benjamin A.
Pu, Jingzhi
Lin, Hai
Zhao, Yan
Truhlar, Donald G.
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2007, 111 (45) : 11706 - 11717
[10] Potential energy surface for a seven-atom reaction.: Thermal rate constants and kinetic isotope effects for CH4+OH
Espinosa-García, J
Corchado, JC
[J]. JOURNAL OF CHEMICAL PHYSICS, 2000, 112 (13) : 5731 - 5739

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