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Quantum instanton calculation of rate constant for CH4 + OH → CH3 + H2O reaction: Torsional anharmonicity and kinetic isotope effect
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10.1063/1.4768874
/content/aip/journal/jcp/137/21/10.1063/1.4768874
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/21/10.1063/1.4768874

Figures

Image of FIG. 1.
FIG. 1.

The geometry for the CH4 + OH → CH3 + H2O reaction at the transition state. Hydroxyl radical can rotate along the C2-H1-O6 axis.

Image of FIG. 2.
FIG. 2.

Arrhenius plots of the thermal rate constants for the CH4+OH reaction. (Solid line) the present QI results; (dashed line) the present QI cl results; (dotted line) the CUS/μOMT results from Ref. 53 ; (dotted-dashed line) the CVT/SCT values; 45 the filled squares, circles, and triangles are corresponding to the experimental values of Vaghjiani and Ravishankara, 38 Sharkey and Smith, 39 and Bryukov et al., 36 respectively.

Image of FIG. 3.
FIG. 3.

Free energy profiles for the CH4+OH reaction along the reaction coordinate at 200 and 800 K. The solid and dashed lines are the quantized and classical free energies, respectively.

Image of FIG. 4.
FIG. 4.

Torsional potential for the internal rotation. The angle of 0 is corresponding to the transition state geometry (the atoms of H3, C2, H1, O6 and H7 are in the same plane).

Image of FIG. 5.
FIG. 5.

The space is divided into three parts by three planes at the transition state geometry of the title reaction. “a,” “b,” and “c” stand for the planes that through the C2-H1-O6 axis and halve the angles of H4-C2-H5, H3-C2-H4, and H3-C2-H5, respectively. In the calculations, the movements of H7 are restricted within the region between “b” and “c.”

Image of FIG. 6.
FIG. 6.

Free energy profiles for the isotopic reactions along the reaction coordinate at 300 K. The solid, dashed, short-dashed, dotted, and dotted-dashed lines are corresponding to the reactions of CH4+OH, CH4+OD, DH2C-H+OH, H3C-D+OH, and CD4+OH, respectively.

Tables

Generic image for table
Table I.

Rate constants for the CH4+OH reaction. a

Generic image for table
Table II.

The torsional anharmonic effect for the internal rotation. a

Generic image for table
Table III.

The kinetic isotope effects (KIEs) at different temperatures.

Generic image for table
Table IV.

The kinetic isotope effects (KIEs) at different temperatures.

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/content/aip/journal/jcp/137/21/10.1063/1.4768874
2012-12-04
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Quantum instanton calculation of rate constant for CH4 + OH → CH3 + H2O reaction: Torsional anharmonicity and kinetic isotope effect
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/21/10.1063/1.4768874
10.1063/1.4768874
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