Communication: Energetics of reaction pathways for reactions of ethenol with the hydroxyl radical: the importance of internal hydrogen bonding at the transition state

The Journal of Chemical Physics
Oksana TishchenkoDonald G Truhlar

Abstract

We find high multireference character for abstraction of H from the OH group of ethenol (also called vinyl alcohol); therefore we adopt a multireference approach to calculate barrier heights for the various possible reaction channels of OH+C(2)H(3)OH. The relative barrier heights of ten possible saddle points for reaction of OH with ethenol are predicted by multireference Møller-Plesset perturbation theory with active spaces based on correlated participating orbitals (CPOs) and CPO plus a correlated pi orbital (CPO+pi). Six barrier heights for abstracting H from a C-H bond range from 3.1 to 7.7 kcal/mol, two barrier heights for abstracting H from an O-H bond are both 6.0 kcal/mol, and two barrier heights for OH addition to the double bond are -1.8 and -2.8 kcal/mol. Thus we expect abstraction at high-temperature and addition at low temperature. The factor that determines which H is most favorable to abstract is an internal hydrogen bond that constitutes part of a six-membered ring at one of the abstraction saddle points; the hydrogen bond contributes about 3 kcal/mol stabilization.

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Citations

Apr 25, 2017·The Journal of Physical Chemistry. a·Miranda F ShawScott H Kable
Jun 3, 2014·Journal of Chemical Information and Modeling·Romina Castañeda-Arriaga, J Raul Alvarez-Idaboy
Dec 3, 2013·Physical Chemistry Chemical Physics : PCCP·Manuel E MedinaJuan Raúl Alvarez-Idaboy
Jun 5, 2012·Chemical Society Reviews·Luc Vereecken, Joseph S Francisco
Jul 8, 2011·Physical Chemistry Chemical Physics : PCCP·Stefania Di TommasoCarlo Adamo
Nov 5, 2010·Journal of the American Chemical Society·Steve Scheiner, Tapas Kar
May 31, 2011·The Journal of Physical Chemistry. B·Annia GalanoJuan R Alvarez-Idaboy
Nov 29, 2013·Journal of the American Chemical Society·Stephen J KlippensteinDonald G Truhlar
Mar 20, 2019·The Journal of Physical Chemistry. a·Xiaoyang LeiWenliang Wang

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