TY - JOUR
T1 - Computational Kinetics by Variational Transition-State Theory with Semiclassical Multidimensional Tunneling
T2 - Direct Dynamics Rate Constants for the Abstraction of H from CH3OH by Triplet Oxygen Atoms
AU - Meana-Paneda, Rubén
AU - Xu, Xuefei
AU - Ma, He
AU - Truhlar, Donald G.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/3/2
Y1 - 2017/3/2
N2 - Rate constants and the product branching ratio for hydrogen abstraction from CH3OH by O(3P) were computed with multistructural variational transition-state theory including microcanonically optimized multidimensional tunneling. Benchmark calculations of the forward and reverse classical barrier heights and the reaction energetics have been carried out by using coupled cluster theory and multireference calculations to select the most reliable density functional method for direct dynamics computations of the rate constants. The dynamics calculations included the anharmonicity of the zero-point energies and partition functions, with specific-reaction-parameter scaling factors for reactants and transition states, and multistructural torsional anharmonicity was included for the torsion around the C-O bond in methanol and in the transition states. The resulting rate constants are presented over a wider range than they are available from experiment, but in the temperature range where experiments are available, they agree well with experimental values, which is encouraging for their reliability over the wider temperature range and for future computations of oxygen atom reaction rates. In contrast to a previous computational prediction, the branching ratio predicted by the present work shows that the formation of CH2OH + OH is the dominant channel over the whole range of temperature from 250 to 2000 K.
AB - Rate constants and the product branching ratio for hydrogen abstraction from CH3OH by O(3P) were computed with multistructural variational transition-state theory including microcanonically optimized multidimensional tunneling. Benchmark calculations of the forward and reverse classical barrier heights and the reaction energetics have been carried out by using coupled cluster theory and multireference calculations to select the most reliable density functional method for direct dynamics computations of the rate constants. The dynamics calculations included the anharmonicity of the zero-point energies and partition functions, with specific-reaction-parameter scaling factors for reactants and transition states, and multistructural torsional anharmonicity was included for the torsion around the C-O bond in methanol and in the transition states. The resulting rate constants are presented over a wider range than they are available from experiment, but in the temperature range where experiments are available, they agree well with experimental values, which is encouraging for their reliability over the wider temperature range and for future computations of oxygen atom reaction rates. In contrast to a previous computational prediction, the branching ratio predicted by the present work shows that the formation of CH2OH + OH is the dominant channel over the whole range of temperature from 250 to 2000 K.
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U2 - 10.1021/acs.jpca.6b10600
DO - 10.1021/acs.jpca.6b10600
M3 - Article
C2 - 28140597
AN - SCOPUS:85027046851
SN - 1089-5639
VL - 121
SP - 1693
EP - 1707
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 8
ER -