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New ab initio potential energy surface for BrH2 and rate constants for the H + HBr → H2 + Br abstraction reaction
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10.1063/1.3563750
/content/aip/journal/jcp/134/11/10.1063/1.3563750
http://aip.metastore.ingenta.com/content/aip/journal/jcp/134/11/10.1063/1.3563750

Figures

Image of FIG. 1.
FIG. 1.

Contour plot of the PES in the entrance valley of the H + HBr → H2 + Br abstraction reaction, as a function of the reactant Jacobi coordinates R and γ with r = 1.403 bohr. The contour interval is 0.05 kcal/mol.

Image of FIG. 2.
FIG. 2.

(upper panel) Contour plot of the PES in the collinear barrier region for the H + HBr → H2 + Br abstraction reaction, as a function of the internal coordinates R HH and R HBr. (lower panel) a close-up of the upper panel in the transition state region. The contour intervals are 0.2 and 0.002 eV for the upper and lower panels, respectively.

Image of FIG. 3.
FIG. 3.

Contour plot of the PES in the exit channel for the H + HBr → H2 + Br abstraction reaction, as a function of the product Jacobi coordinates R p and α with optimized r p for each pair of R p and α. The contour interval is 0.05 kcal/mol.

Image of FIG. 4.
FIG. 4.

(upper panel) Contour plot of the PES in the collinear barrier region for the H + H′Br → H′ + HBr exchange reaction, as a function of the internal coordinates R H′Br and R HBr. (lower panel) a close-up of the upper panel in the transition state region. The contour intervals are 0.2 and 0.01 eV for the upper and lower panels, respectively.

Image of FIG. 5.
FIG. 5.

One dimensional curve of SO correction as a function of the product Jacobi coordinates R p with r p = 2.4 bohr and α = 0°. A close-up of the barrier region is extracted and highlighted with red in the right corner of the plot.

Image of FIG. 6.
FIG. 6.

One-dimensional curve of the spin–orbit correction as a function of the product Jacobi coordinates α. R p and r p are fixed at 6.0 and 1.4 bohr, respectively.

Image of FIG. 7.
FIG. 7.

Total reaction probabilities for J = 0 partial wave of the H + HBr(ν i = 0, j i = 0) reaction as a function of collision energy (E c).

Image of FIG. 8.
FIG. 8.

The initial state selected rate constants for the H + HBr(ν i = 0, j i = 0) → H2+ Br abstraction reaction with comparison with existing theoretical and experimental data.

Tables

Generic image for table
Table I.

Estimated barrier heights and exothermicities (in kcal/mol) for the H + HBr → H2 + Br abstraction reaction without the spin–orbit coupling, obtained from various basis sets and the complete basis limit.

Generic image for table
Table II.

Calculated spectroscopic constants for the diatomic molecules with comparison with experimental values.

Generic image for table
Table III.

Calculated and observed exoergic energies (in kilocalorie per mol) for the H + HBr → H2 + Br reaction.

Generic image for table
Table IV.

Comparison of various BrH2 PESs in the vdW well region in the entrance channel. The optimized geometry is in the internal coordinates (R HH, R HBr, θ) and the well depth is relative to the H + HBr asymptote. (Bond distance in bohr, bond angle in degree, well depth in kilocalorie per mol , and harmonic frequency in per centimeter).

Generic image for table
Table V.

Comparison of the barrier characteristics for the H + HBr abstraction reaction. The optimized geometry is in the internal coordinates (R HH, R HBr, θ) and the barrier height is relative to the H + HBr asymptote. (Bond distance in bohr, bond angle in degree, barrier height in kilocalorie per mol and harmonic frequency in per centimeter).

Generic image for table
Table VI.

Comparison of the barrier characteristics for the H + H′Br exchange reaction. The optimized geometry is in the internal coordinates (R HH, R HBr, θ) and the barrier height is relative to the H + HBr asymptote. (Bond distance in bohr, bond angle in degree, barrier height in kilocalorie per mol and harmonic frequency in centimeter).

Generic image for table
Table VII.

Numerical parameters used in the wave packet calculations. (Atomic units are used unless stated otherwise.)

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/content/aip/journal/jcp/134/11/10.1063/1.3563750
2011-03-15
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: New ab initio potential energy surface for BrH2 and rate constants for the H + HBr → H2 + Br abstraction reaction
http://aip.metastore.ingenta.com/content/aip/journal/jcp/134/11/10.1063/1.3563750
10.1063/1.3563750
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