Distribution of ab initio data as a function of energy relative to the global minimum, namely, the pre-reaction van der Waals complex.
Schematic illustration of the reaction pathway for the O + H2O → 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 + H2O asymptote. TS′ was optimized at the UCCSD(T)-FC/AVTZ and the energies were obtained at the UCCSD(T)-FU/AVTZ level.
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.
Top panel: minimum energy path, V MEP, zero point energy, ZPE, and vibrationally adiabatic ground state energy (all energies in kcal/mol) as a function of the reaction coordinate s; Middle panel: generalized normal mode vibrational frequencies (cm−1) as a function of s; Bottom panel: geometry of the MEP as a function of s.
Top panel: coupling terms, B mF, between the first three vibrational modes and the reaction mode; bottom panel: the reaction path curvature, κ, as a function of the reaction coordinate s.
Canonical rate constants for the forward (upper panel) and reverse (lower panel) directions of the title reaction with comparison to the recommended experimental values. 10,18
Opacity function for the title reaction in forward direction at E c = 25 kcal/mol.
Product angular distributions (DCS) for the title reaction in forward direction at E c = 25 kcal/mol.
Rotational state distribution of the “nascent” OH (top) and the “spectator” one (bottom) at their vibrational ground state.
Optimized geometries (in internal coordinates, lengths in Å and angles in °) of the stationary points for O(3P) + H2O → OH + OH using various electronic structure methods.
Comparison of classical reaction energies and barriers using different electronic structure methods.
Classical energies (in kcal/mol relative to the reactant asymptote) and frequencies (cm−1) of the stationary points for the O + H2O → OH + OH reaction.
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