Theoretical Kinetics Study of the O(3P) + CH4/CD4 Hydrogen Abstraction Reaction: The Role of Anharmonicity, Recrossing Effects, and Quantum Mechanical Tunneling

被引:57
作者
Gonzalez-Lavado, Eloisa [1 ]
Corchado, Jose C. [1 ]
Suleimanov, Yury V. [2 ,3 ]
Green, William H. [2 ]
Espinosa-Garcia, Joaquin [1 ]
机构
[1] Univ Extremadura, Dept Quim Fis, E-06071 Badajoz, Spain
[2] MIT, Dept Chem Engn, Cambridge, MA 02139 USA
[3] Princeton Univ, Dept Mech & Aerosp Engn, Combust Energy Frontier Res Ctr, Princeton, NJ 08544 USA
关键词
POLYMER MOLECULAR-DYNAMICS; TRANSITION-STATE THEORY; CHEMICAL-REACTION RATES; RATE CONSTANTS; RATE COEFFICIENTS; QUANTUM DYNAMICS; ATOMIC OXYGEN; METHANE; HYDROGEN; ABSTRACTION;
D O I
10.1021/jp5028965
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
Using a recently developed full-dimensional accurate analytical potential energy surface [Gonzalez-Lavado, E.; Corchado, J. C.; Espinosa-Garcia, J. J. Chem. Phys. 2014, 140, 064310], we investigate the thermal rate coefficients of the O(P-3) + CH4/CD4 reactions with ring polymer molecular dynamics (RPMD) and with variational transition-state theory with multidimensional tunneling corrections (VTST/MT). The results of the present calculations are compared with available experimental data for a wide temperature range 200-2500 K. In the classical high-temperature limit, the RPMD results match perfectly the experimental data, whereas VTST results are smaller by a factor of 2. We suggest that this discrepancy is due to the harmonic approximation used in the present VTST calculations, which leads to an overestimation of the variational effects. At low temperatures the tunneling plays an important role, which is captured by both methods, although they both overestimate the experimental values. The analysis of the kinetic isotope effects shows a discrepancy between both approaches, with the VTST values smaller by a factor about 2 at very low temperatures. Unfortunately, no experimental results are available to shed any light on this comparison, which keeps it as an open question.
引用
收藏
页码:3243 / 3252
页数:10
相关论文
共 62 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] [Anonymous], 18 S INT COMB
  • [3] [Anonymous], INT J CHEM KINET
  • [4] [Anonymous], 15 S INT COMB
  • [5] Barassin J., 1974, J B SOC CHIM FR, V1, P1
  • [6] EVALUATED KINETIC DATA FOR COMBUSTION MODELING
    BAULCH, DL
    COBOS, CJ
    COX, RA
    ESSER, C
    FRANK, P
    JUST, T
    KERR, JA
    PILLING, MJ
    TROE, J
    WALKER, RW
    WARNATZ, J
    [J]. JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1992, 21 (03) : 411 - 734
  • [7] ESR STUDIES OF REACTIONS OF ATOMIC OXYGEN AND HYDROGEN WITH SIMPLE HYDROCARBONS
    BROWN, JM
    THRUSH, BA
    [J]. TRANSACTIONS OF THE FARADAY SOCIETY, 1967, 63 (531P): : 630 - &
  • [8] KINETICS OF REACTION OF O(3P) WITH METHANE IN OXYGEN NITROGEN AND ARGON-OXYGEN MIXTURES
    CADLE, RD
    ALLEN, ER
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1965, 69 (05) : 1611 - &
  • [9] Reaction-path dynamics in redundant internal coordinates
    Chuang, YY
    Truhlar, DG
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (01) : 242 - 247
  • [10] Clary P. C., 1999, PHYS CHEM CHEM PHYS, V1, P1173