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An improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: Application to the hydrogen abstraction reactions , , , and
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10.1063/1.3177380
/content/aip/journal/jcp/131/4/10.1063/1.3177380
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/4/10.1063/1.3177380

Figures

Image of FIG. 1.
FIG. 1.

Schematic representation of the partitioning of the Hessian involved in the determination of .

Image of FIG. 2.
FIG. 2.

Schematic representation of the systems.

Image of FIG. 3.
FIG. 3.

Number of postprojection imaginary frequencies for the reaction in rectilinear coordinates plotted as a function of the hyperspherical coordinates. The solid lines are contours of the underlying PES, shown as a guide to the eye (plotted for energies up to ).

Image of FIG. 4.
FIG. 4.

The frequencies of selected symmetry breaking modes along the MEP. The panels are (from top to bottom) for , H, D. The dashed lines correspond to the postprojection frequencies in rectilinear coordinates, and the solid lines to postprojection frequencies in curvilinear coordinates. Note that the reaction coordinate in the top panel has been scaled up by a factor of 2 for ease of plotting.

Image of FIG. 5.
FIG. 5.

The difference in ZPEs of the spectator mode postprojection calculated as , where and represent curvilinear and rectilinear coordinates, respectively. The color is an indication of height and the same scale is used for each reaction for comparison. It is seen that differences are greatest for and smallest, on average, for . The scale on the color bar is in , is in radians and in . Each plot includes a contour plot of the appropriate PES as a guide [plotted for energies up to and ].

Image of FIG. 6.
FIG. 6.

Thermal rate constants for reaction (1), . References are given in the text.

Image of FIG. 7.
FIG. 7.

Thermal rate constants for reaction (2), . References are given in the text.

Image of FIG. 8.
FIG. 8.

KIEs (using curvilinear coordinates). The experimental data are evaluated by combining the rates for reaction (2) from Snooks et al. (Ref. 54) with the rates for reaction (1) from Refs. 18 and 23. Other data are taken from Refs. 56 and 55.

Image of FIG. 9.
FIG. 9.

Thermal rate constants for reaction (3), . References are given in the text.

Image of FIG. 10.
FIG. 10.

H/D KIEs (using curvilinear coordinates). The experimental data is taken from Ref. 21. Other data are from Refs. 56, 55, and 58.

Image of FIG. 11.
FIG. 11.

Thermal rate constants for reaction (4), , compared to experimental (Ref. 59) and VTST (Ref. 60) data.

Tables

Generic image for table
Table I.

Surface parameters: column headings refer to the abstracting species with spectator modes treated in either curvilinear or rectilinear coordinates. is the number of ab initio grid points and SSR is the sum of squared residuals for the fit.

Generic image for table
Table II.

Single point CCSD(T)/cc-pVTZ//MP2/cc-pVTZ energies and ab initio (unprojected) reaction surface characteristics. and are the classical energy of reaction and enthalpy of reaction, respectively. and are the classical and ZPE corrected barrier heights.

Generic image for table
Table III.

Symmetry numbers and moments of inertia required for evaluating rotational partition functions (multiplicities in parentheses).

Generic image for table
Table IV.

Frequencies in for the TSs and all relevant asymptotic species, calculated at MP2/cc-pVTZ (parentheses indicate multiplicities). For completeness, imaginary frequencies are included in the preprojection TS data.

Generic image for table
Table V.

Rate constants for reactions (1)–(4). Column heading refer to the species X with either curvilinear or rectilinear treatment of the spectator modes. All values are in .

Generic image for table
Table VI.

H/D and KIEs.

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/content/aip/journal/jcp/131/4/10.1063/1.3177380
2009-07-24
2014-04-23
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: An improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: Application to the hydrogen abstraction reactions μ+CH4, H+CH4, D+CH4, and CH3+CH4
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/4/10.1063/1.3177380
10.1063/1.3177380
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