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Combined valence bond-molecular mechanics potential-energy surface and direct dynamics study of rate constants and kinetic isotope effects for the reaction
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10.1063/1.2132276
/content/aip/journal/jcp/124/4/10.1063/1.2132276
http://aip.metastore.ingenta.com/content/aip/journal/jcp/124/4/10.1063/1.2132276

Figures

Image of FIG. 1.
FIG. 1.

Transition state geometry for the reaction.

Image of FIG. 2.
FIG. 2.

Rotational barrier (in ) of the transition state for the reaction at the MPW54/6-31 level.

Image of FIG. 3.
FIG. 3.

for the four reactions as a function of reaction coordinate obtained using the MPW54/6-31 level with the HR approximation.

Image of FIG. 4.
FIG. 4.

Logarithm of the deuterium KIE for reactions (R1) and (R2) vs obtained using the MPW54/6-31 level with the HR approximation. is for and is for .

Image of FIG. 5.
FIG. 5.

Logarithm of the deuterium KIE for reactions (R1) and (R3) vs obtained using the MPW54/6-31 level with the HR approximation. is for and is for .

Image of FIG. 6.
FIG. 6.

Logarithm of the deuterium KIE for reactions (R1) and (R4) vs obtained using the MPW54/6-31 level with the HR approximation. is for and is for .

Image of FIG. 7.
FIG. 7.

Comparison of the plot of for the reaction as a function of reaction coordinate obtained by using the CVBMM surface and the MPW54/6-31 level.

Image of FIG. 8.
FIG. 8.

Comparison of the plot of for the reaction as a function of reaction coordinate obtained by using the CVBMM surface and the MPW54/6-31 level.

Tables

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Table I.

Energetics for the reaction . is the forward classical barrier height, is the reverse classical barrier height, and is the classical energy of reaction.

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Table II.

ZPEs, differences in ZPE between saddle point and reactants and between saddle point and products, ground-state vibrationally adiabatic barrier height at the saddle point, and enthalpy of reaction at 0 K.

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Table III.

Comparison of calculated barrier heights for and reactions.

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Table IV.

Geometries and imaginary frequencies for the saddle point. Distances are in Å, bond angles are in deg, and frequencies are in .

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Table V.

Direct dynamics rate constants for the reaction. The 6-31 basis set used. HO denotes the harmonic-oscillator approximation for all modes; HR denotes that the lowest-frequency mode is treated as a hindered rotator.

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Table VI.

Direct dynamics rate constants for the , and reactions All calculations in this table use the MPW 54/6-31 electronic structure level and use the HR approximation for the lowest-frequency mode.

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Table VII.

KIEs and factors for the . All calculations in this table use the MPW 54/6-31 electronic structure level with the HR approximation for the torsion mode.

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Table VIII.

Optimized geometries of the stationary points for the reaction obtained from the CVBMM potential-energy surface. Distances are in Å and angles are in deg.

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Table IX.

Normal-mode analysis of the stationary points of the CVBMM potential-energy surface of the reaction.

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Table X.

Rate constants obtained using the CVBMM surface for the reaction.

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/content/aip/journal/jcp/124/4/10.1063/1.2132276
2006-01-27
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Combined valence bond-molecular mechanics potential-energy surface and direct dynamics study of rate constants and kinetic isotope effects for the H+C2H6 reaction
http://aip.metastore.ingenta.com/content/aip/journal/jcp/124/4/10.1063/1.2132276
10.1063/1.2132276
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