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Direct-dynamics VTST study of hydrogen or deuterium abstraction and C–C bond formation or dissociation in the reactions of CH3 + CH4, CH3 + CD4, CH3D + CD3, CH3CH3 + H, and CH3CD3 + D
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10.1063/1.4803862
/content/aip/journal/jcp/138/19/10.1063/1.4803862
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/19/10.1063/1.4803862

Figures

Image of FIG. 1.
FIG. 1.

Relative energies of different species for all the reactions in kJ mol at the CCSD(T)/6-311++G(2df,2p) level. All values are corrected for zero point energies.

Image of FIG. 2.
FIG. 2.

Optimized structure of the stationary points at the MP2/6-311++G(d,p) level for all reactions, lengths in angstrom, and angle in degree.

Image of FIG. 3.
FIG. 3.

Ground-state vibrationally adiabatic potential , potential minimum energy path (V), and zero point energy (ZPE), for the (R1) reaction (dotted line), (R5) reaction (open circle), (R6) reaction (solid line), and (R7) reaction (square).

Image of FIG. 4.
FIG. 4.

Ground-state vibrationally adiabatic potential for the (R1) reaction (dashed line), (R5) reaction (circle), (R6) reaction (dotted line), and (R7) reaction (solid line). The straight lines indicate the representative tunneling energy at 298.0 K.

Image of FIG. 5.
FIG. 5.

Thermally averaged transmission probability at 298 with SCT calculation for (R1) (solid line), (R5) (open circle), (R6) (dotted line), and (R7) (dashed line).

Image of FIG. 6.
FIG. 6.

Generalized frequencies at the MPWBLK/6-311++G** level along the reaction coordinate. ω in (R1) (solid line), ω in (R5) (dotted line), ω in (R6) (dashed line), ω in (R7) (dashed-dotted line), and ω in (R7)(dashed-dotted-dotted line).

Image of FIG. 7.
FIG. 7.

Variation of the curvature parameter (B) along the reaction coordinate, for (R1) reaction (dotted line), (R5) reaction (dashed line), (R6) reaction (open squares), and (R7) reaction (solid line).

Image of FIG. 8.
FIG. 8.

Arrhenius plot of the calculated rate constants in this work by the CVT/SCT and CVT/LCT for (R1) and (R5) reactions. The experimental values are also plotted for comparison.

Image of FIG. 9.
FIG. 9.

Arrhenius plot of the calculated rate constants in this work by the CVT/SCT and CVT/LCT for (R2) reaction. The experimental values are also plotted for comparison.

Image of FIG. 10.
FIG. 10.

Arrhenius plot of the calculated CVT/SCT rate constants in this work for all channels.

Image of FIG. 11.
FIG. 11.

Generalized frequencies at the MPWB1K/6-311++G** level along the reaction coordinate. ω in (R2) (solid line), ω in (R8) (dotted line), ω in (R9) (dashed-dotted line), and ω in (R10) (dashed-dotted-dotted line).

Image of FIG. 12.
FIG. 12.

Generalized frequencies at the MPWB1K/6-311++G** level along the reaction coordinate. ω in (R3) (solid line), ω in (R11) (dotted line), and ω in (R12) (dashed line).

Image of FIG. 13.
FIG. 13.

Generalized frequencies at the MPWB1K/6-311++G** level along the reaction coordinate. ω in (R4) (solid line), ω in (R13) (dotted line), and ω in (R14) (dashed line).

Tables

Generic image for table
Table I.

Calculated primary kinetic isotope effect in (R1) and (R5) reactions ( / ).

Generic image for table
Table II.

Calculated primary kinetic isotope effect in (R1) and (R6) reactions ( / ).

Generic image for table
Table III.

Calculated primary kinetic isotope effect in (R1) and (R7) reactions ( / ).

Generic image for table
Table IV.

The fitted parameters using Arrhenius equations for reactions (R1)–(R14) in the temperature range T = 200–2900 K.

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/content/aip/journal/jcp/138/19/10.1063/1.4803862
2013-05-20
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Direct-dynamics VTST study of hydrogen or deuterium abstraction and C–C bond formation or dissociation in the reactions of CH3 + CH4, CH3 + CD4, CH3D + CD3, CH3CH3 + H, and CH3CD3 + D
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/19/10.1063/1.4803862
10.1063/1.4803862
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