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Chemical reaction surface vibrational frequencies evaluated in curvilinear internal coordinates: Application to
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10.1063/1.3052076
/content/aip/journal/jcp/130/2/10.1063/1.3052076
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/2/10.1063/1.3052076

Figures

Image of FIG. 1.
FIG. 1.

A schematic of vibrational paths away from the reaction surface (for clarity this diagram uses and so the surface is just the MEP). The black line represents the MEP while the red and blue lines represent different harmonic curves with the same geometry at their minima but different geometries away from . The view on the right is looking down on the MEP from above and highlights the curved path followed by the red line relative to the straight line motion of the blue vibration. The coincidence of the two vibrations on the MEP indicates that all points on the red and blue paths correspond to the same MEP geometry. As the geometries permitted by harmonic expansion are determined by the coordinate frame it is clear that this is equivalent to the definition of for points away from the MEP.

Image of FIG. 2.
FIG. 2.

Schematic representation of the system.

Image of FIG. 3.
FIG. 3.

: the difference between the ZPEs of the spectator modes calculated with curvilinear and rectilinear projection. The energy difference, in Hartree, is plotted for a number of values of and across the reaction surface. Points in red are for and points in blue are for . The translucent plane is set at as a guide to the eye.

Image of FIG. 4.
FIG. 4.

Thermal rate constants for reaction (R1). The experimental data are taken from Ref. 22.

Image of FIG. 5.
FIG. 5.

Thermal rate constants for reaction (R1) compared with results from experiments and previous theoretical studies (references given in the text).

Image of FIG. 6.
FIG. 6.

Thermal rate constants for reaction (R2) compared with results from experiments and previous theoretical studies (references given in the text).

Tables

Generic image for table
Table I.

Geometries of the asymptotic species and TS [the same for (R1) and (R2)], optimized at MP2/cc-pVTZ. Angles are in degrees and distances in . is the incoming H atom in (R1) and is the abstracted H atom in that reaction. The TS has symmetry.

Generic image for table
Table II.

Single point CCSDT(T)/cc-pVTZ//MP2/cc-pVTZ energies.

Generic image for table
Table III.

Parameters defining potential energy surfaces including spectator mode ZPE corrections evaluated via projection in curvilinear and rectilinear coordinates.

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Table IV.

Frequencies in for the TS and all relevant asymptotic species, calculated at MP2/cc-pVTZ (parentheses indicate multiplicities).

Generic image for table
Table V.

Spectator mode frequencies for the reaction surface geometry corresponding to and . Frequencies are quoted after projection in both rectilinear and curvilinear coordinates (see text). The frequencies are listed in order of increasing absolute value.

Generic image for table
Table VI.

Thermal rate constants (in ) for reaction (R1) evaluated on a PES adiabatically corrected with spectator mode ZPEs: indicates curvilinear projection and indicates rectilinear projection.

Generic image for table
Table VII.

Thermal rate constants (in ) for reaction (R2) evaluated on a PES adiabatically corrected with spectator mode ZPEs: indicates curvilinear projection and indicates rectilinear projection.

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/content/aip/journal/jcp/130/2/10.1063/1.3052076
2009-01-13
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Chemical reaction surface vibrational frequencies evaluated in curvilinear internal coordinates: Application to H+CH4⇌H2+CH3
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/2/10.1063/1.3052076
10.1063/1.3052076
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