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Potential energy surface, kinetics, and dynamics study of the reaction
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10.1063/1.2179067
/content/aip/journal/jcp/124/12/10.1063/1.2179067
http://aip.metastore.ingenta.com/content/aip/journal/jcp/124/12/10.1063/1.2179067

Figures

Image of FIG. 1.
FIG. 1.

Arrhenius plots of for the forward thermal rate constants against the reciprocal of temperature (K) in the range . Solid and dashed lines, our VTST values for the PES-2005 and PES-2000 surfaces, respectively. Experimental values as symbols: + (Ref. 42), ▵ (Ref. 43), 엯 (Ref. 44), and ◻ (Refs. 3, 6, and 47).

Image of FIG. 2.
FIG. 2.

Saddle point bending-energy curves (C–H–Cl) for the reaction. The remaining internal coordinates have been kept fixed for the respective methods. Solid and dashed lines, our values for the PES-2005 and PES-2000 surfaces, respectively. Dotted line, CCSD(T)/cc-pVTZ ab initio calculations; dashed-dotted line, ab initio calculations, and dashed-triple point line, ab initio calculations. Note that the value of 180° corresponds to the saddle point.

Image of FIG. 3.
FIG. 3.

Contour plots of the saddle point zone for the PES-2005 surface (first panel), PES-2000 surface (second panel), ab initio level (third panel), and ab initio level (fourth panel). The symbols ×, ▵, 엯, and ◻ mean the respective saddle point at each level. The contours are shown at increments, with the maximum value at the saddle point. When in a panel a symbol does not appear, this means that it is outside the represented range of distances. The axis labels are the same for the four plots.

Image of FIG. 4.
FIG. 4.

Reaction-path curvature as a function of reaction coordinate .

Image of FIG. 5.
FIG. 5.

Theoretical (◻, this work) and experimental (●, Ref. 13; ▴, Ref. 61) KIEs at as a function of the number of substituted hydrogens, .

Image of FIG. 6.
FIG. 6.

Rotational populations for the reaction, which are computed using histogram binning taking into account all the reactive trajectories (엯), histogram binning with simple ZPE correction (◻), Gaussian binning (×), histogram binning with double ZPE correction (◇), and histogram binning with simple ZPE correction and truncated values (▵). The distributions are normalized so that the area under the common levels is the same. The figure has been divided into two panels for clarity.

Image of FIG. 7.
FIG. 7.

Rotational populations for (a) and (b) . Dashed lines are experimental values from Refs. 5 (●), 7 (∎), 8 (▴), and 97 (◆), and solid lines are theoretical values from this work (◻), Refs. 92 and 93 (▵), and Ref. 96 (엯). The distributions are normalized so that the area under the common levels is the same.

Image of FIG. 8.
FIG. 8.

Product angular distribution for the reaction, with .

Image of FIG. 9.
FIG. 9.

Product angular distributions for (a) and (b) . Dashed lines are experimental values from Refs. 5 (●) and 97 (◆), and solid lines are theoretical values from this work (◻) and Refs. 92 and 93 (▵). The scattering distributions are normalized so that the area under the common regions is the same.

Image of FIG. 10.
FIG. 10.

Rotational populations for the . The dashed line represents experimental values from Ref. 4 (●), and solid lines are theoretical values from this work using the HB-ZPE binning procedure (◻), the double ZPE binning procedure (◇), and Ref. 96 (엯). The distributions are normalized so that the area under the common levels is the same.

Image of FIG. 11.
FIG. 11.

Rotational populations for . The dashed line represents experimental values from Ref. 4 (●), and solid lines are theoretical values from this work using the HB-ZPE binning procedure (◻), the double ZPE binning procedure (◇), Refs. 92 and 93 (▵), and Ref. 96 (엯). The distributions are normalized so that the area under the common levels is the same.

Image of FIG. 12.
FIG. 12.

Product angular distributions for . The dashed line represents experimental values from Ref. 4 (●), and solid lines are theoretical values from this work (◻), Refs. 92 and 93 (▵), and Ref. 96 (엯). The scattering distributions are normalized so that the area under the common regions is the same.

Image of FIG. 13.
FIG. 13.

Product angular distributions for . The dashed line represents experimental values from Ref. 4 (●), and solid lines are theoretical values from this work (◻), Ref. 78 (▵), and Ref. 96 (엯). The scattering distributions are normalized so that the area under the common regions is the same.

Image of FIG. 14.
FIG. 14.

The same as Fig. 13, but for the reaction.

Tables

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Table I.

Reactant and product properties (distances in angstrom, frequencies in ) calculated using the PES-2005 analytical surface.

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Table II.

Saddle point properties.

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Table III.

Thermal forward rate coefficients for the reaction.

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Table IV.

Reverse rate coefficients for the reaction.

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Table V.

kinetic isotope effects for the forward reaction.

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Table VI.

kinetic isotope effects for the forward reaction.

Generic image for table
Table VII.

kinetic isotope effects for the forward reaction.

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Table VIII.

kinetic isotope effects for the forward reaction.

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Table IX.

kinetic isotope effects for the forward reaction.

Generic image for table
Table X.

kinetic isotope effects for the forward reaction.

Generic image for table
Table XI.

Average scattering angle (in degrees) for the reaction.

Generic image for table
Table XII.

PES-2000 vs PES-2005. Kinetics and dynamics comparison.

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/content/aip/journal/jcp/124/12/10.1063/1.2179067
2006-03-24
2014-04-16
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Potential energy surface, kinetics, and dynamics study of the Cl+CH4→HCl+CH3 reaction
http://aip.metastore.ingenta.com/content/aip/journal/jcp/124/12/10.1063/1.2179067
10.1063/1.2179067
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