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A new ab initio based global HOOH(13A″) potential energy surface for the O(3P) + H2O(X1A1) ↔ OH(X2Π) + OH(X2Π) reaction
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10.1063/1.4804418
/content/aip/journal/jcp/138/19/10.1063/1.4804418
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/19/10.1063/1.4804418

Figures

Image of FIG. 1.
FIG. 1.

Distribution of data as a function of energy relative to the global minimum, namely, the pre-reaction van der Waals complex.

Image of FIG. 2.
FIG. 2.

Schematic illustration of the reaction pathway for the O + HO → OH + OH reaction on the lowest triplet state PES. The CCSD(T)-FU/AVTZ energies are given above the corresponding values of the fitted PES, which is in italic. The ZPE corrected values are given in wavy lines. All energies are in kcal/mol and relative to the O + HO asymptote. TS′ was optimized at the UCCSD(T)-FC/AVTZ and the energies were obtained at the UCCSD(T)-FU/AVTZ level.

Image of FIG. 3.
FIG. 3.

Contours of the fitted PES along the two bonds involved in the reaction with all other internal coordinates optimized. The outer one is from 0 to 51 kcal/mol with an interval of 3 kcal/mol, and the inner one, showing details around the transition state, is from 0 to 40 kcal/mol with an interval of 2 kcal/mol.

Image of FIG. 4.
FIG. 4.

Top panel: minimum energy path, , zero point energy, ZPE, and vibrationally adiabatic ground state energy (all energies in kcal/mol) as a function of the reaction coordinate ; Middle panel: generalized normal mode vibrational frequencies (cm) as a function of ; Bottom panel: geometry of the MEP as a function of .

Image of FIG. 5.
FIG. 5.

Top panel: coupling terms, , between the first three vibrational modes and the reaction mode; bottom panel: the reaction path curvature, , as a function of the reaction coordinate .

Image of FIG. 6.
FIG. 6.

Canonical rate constants for the forward (upper panel) and reverse (lower panel) directions of the title reaction with comparison to the recommended experimental values.

Image of FIG. 7.
FIG. 7.

Opacity function for the title reaction in forward direction at = 25 kcal/mol.

Image of FIG. 8.
FIG. 8.

Product angular distributions (DCS) for the title reaction in forward direction at = 25 kcal/mol.

Image of FIG. 9.
FIG. 9.

Rotational state distribution of the “nascent” OH (top) and the “spectator” one (bottom) at their vibrational ground state.

Tables

Generic image for table
Table I.

Optimized geometries (in internal coordinates, lengths in Å and angles in °) of the stationary points for O(P) + HO → OH + OH using various electronic structure methods.

Generic image for table
Table II.

Comparison of classical reaction energies and barriers using different electronic structure methods.

Generic image for table
Table III.

Classical energies (in kcal/mol relative to the reactant asymptote) and frequencies (cm) of the stationary points for the O + HO → OH + OH reaction.

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/content/aip/journal/jcp/138/19/10.1063/1.4804418
2013-05-16
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A new ab initio based global HOOH(13A″) potential energy surface for the O(3P) + H2O(X1A1) ↔ OH(X2Π) + OH(X2Π) reaction
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/19/10.1063/1.4804418
10.1063/1.4804418
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