Full-Dimensional Quantum Reaction Rate Calculations for H + CH4 → H2 + CH3 on a Recent Potential Energy Surface

被引：47

作者：

Schiffel, Gerd ^{[2
]}

Manthe, Uwe ^{[2
]}

Nyman, Gunnar ^{[1
]}

机构：

[1] Univ Gothenburg, Dept Chem, SE-41296 Gothenburg, Sweden

[2] Univ Bielefeld, Fak Chem, D-33615 Bielefeld, Germany

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2010年 / 114卷 / 36期

基金：

瑞典研究理事会;

关键词：

THERMAL RATE CONSTANTS; REDUCED-DIMENSIONALITY; PROPAGATING WAVEPACKETS; CH3+H-2 REACTION; H+CH4 REACTION; DYNAMICS; METHANE; TEMPERATURE; ABSTRACTION; SCATTERING;

D O I：

10.1021/jp911880u

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：

The thermal rate constant of the H + CH4 -> H-2 + CH3 reaction on the recent potential energy surface (PES) of Corchado et al (CBE) (Corchado, J. C.; Bravo, J. L.; Espinosa-Garcia, J. J. Chem. Phys. 2009, 130, 184-314) is computed employing the state-averaged multiconfigurational time-dependent Hartree approach in the temperature range 250-500 K. The CBE PES is global and is based on an analytic functional form that is fast to evaluate. This surface is therefore potentially useful for testing new quantum dynamics methods, and reference rate constants for this purpose are presented here. The thermal rate constants obtained are compared to results previously obtained on an accurate PES particularly designed for thermal rate constant calculations (Wu, T.; Werner, H.; Manthe, U. Science 2004, 306, 2227). The two sets of rate constants are found to agree almost perfectly.

引用

页码：9617 / 9622

页数：6

共 39 条

[1] EFFECT OF IRRADIATION TEMPERATURE ON THE RADIOLYSIS OF METHANE [J].

ARAI, H ;

NAGAI, S ;

MATSUDA, K ;

HATADA, M .

RADIATION PHYSICS AND CHEMISTRY, 1981, 17 (03) :151-157

[2] MERCURY-PHOTOSENSITIZED DECOMPOSITION OF METHANE [J].

BACK, RA ;

VANDERAUWERA, D .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1962, 40 (12) :2339-&

[3] The multiconfiguration time-dependent Hartree (MCTDH) method:: a highly efficient algorithm for propagating wavepackets [J].

Beck, MH ;

Jäckle, A ;

Worth, GA ;

Meyer, HD .

PHYSICS REPORTS-REVIEW SECTION OF PHYSICS LETTERS, 2000, 324 (01) :1-105

[4] KINETICS OF THE REACTION H+CH4=CH3+H2 [J].

BERLIE, MR ;

LEROY, DJ .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1954, 32 (07) :650-659

[5] REDUCED DIMENSIONALITY THEORY OF QUANTUM REACTIVE SCATTERING [J].

BOWMAN, JM .

JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (13) :4960-4968

[6] The importance of an accurate CH4 vibrational partition function in full dimensionality calculations of the H+CH4→H2+CH3 reaction [J].

Bowman, JM ;

Wang, DY ;

Huang, XC ;

Huarte-Larrañaga, F ;

Manthe, U .

JOURNAL OF CHEMICAL PHYSICS, 2001, 114 (21) :9683-9684

[7] The hydrogen abstraction reaction H+CH4. I. New analytical potential energy surface based on fitting to ab initio calculations [J].

Corchado, Jose C. ;

Bravo, Jose L. ;

Espinosa-Garcia, Joaquin .

JOURNAL OF CHEMICAL PHYSICS, 2009, 130 (18)

[8] The ground state tunneling splitting of malonaldehyde: Accurate full dimensional quantum dynamics calculations [J].

Coutinho-Neto, MD ;

Viel, A ;

Manthe, U .

JOURNAL OF CHEMICAL PHYSICS, 2004, 121 (19) :9207-9210

[9] New analytical potential energy surface for the CH4+H hydrogen abstraction reaction:: Thermal rate constants and kinetic isotope effects [J].

Espinosa-García, J .

JOURNAL OF CHEMICAL PHYSICS, 2002, 116 (24) :10664-10673

[10]

GAUSS J, IN PRESS

← 1 2 3 4 →