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Kinetics of the Hydrogen Abstraction Reaction From 2-Butanol by OH Radical

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [1];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
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The kinetics of the hydrogen abstraction from 2-butanol by hydroxyl radical have been studied using multipath variational transition-state theory with the multidimensional small curvature tunneling approximation. The rate constants for each of the five hydrogen abstraction sites (C1, C2, C3, C4, and O) and the overall reaction have been computed by direct dynamics based on M08-HX/6-311+G(2df,2p) electronic structure calculations. Here, we show that multistructural torsional anharmonicity, anharmonicity differences of high-frequency modes between the transition structures and the reactants, and reaction-path dependence of multiple reaction paths are all important factors for determining accurate reaction rates and branching fractions for this problem. The reaction barrier heights for abstraction from various sites follow the order C2 < C3 < C4 < C1 < O, but the reactivities of the various sites do not precisely follow the inverse order of barrier heights, and the order of reactivities depends on temperature. Thus, the abstractions from C2 and C3 have the largest contribution to the total reaction rate from 200 to 2000 K.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Combustion Energy Frontier Research Center (CEFRC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
FG02-86ER13579; SC0001198
OSTI ID:
1369834
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 50 Vol. 119; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Perspective: Kohn-Sham density functional theory descending a staircase journal October 2016

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