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Alkyl hydrogen atom abstraction reactions of the CN radical with ethanol

Athokpam, Bijyalaxmi and Ramesh, Sai G (2018) Alkyl hydrogen atom abstraction reactions of the CN radical with ethanol. In: JOURNAL OF CHEMICAL PHYSICS, 148 (13).

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Official URL: http://dx.doi.org/10.1063/1.5021634

Abstract

We present a study of the abstraction of alkyl hydrogen atoms from the beta and alpha positions of ethanol by the CN radical in solution using the Empirical Valence Bond (EVB) method. We have built separate 2 x 2 EVB models for the H-beta and H-alpha reactions, where the atom transfer is parameterized using ab initio calculations. The intra- and intermolecular potentials of the reactant and product molecules were modelled with the General AMBER Force Field, with some modifications. We have carried out the dynamics in water and chloroform, which are solvents of contrasting polarity. We have computed the potential of mean force for both abstractions in each of the solvents. They are found to have a small and early barrier along the reaction coordinate with a large energy release. Analyzing the solvent structure around the reaction system, we have found two solvents to have little effect on either reaction. Simulating the dynamics from the transition state, we also study the fate of the energies in the HCN vibrational modes. The HCN molecule is born vibrationally hot in the CH stretch in both reactions and additionally in the HCN bends for the H-alpha abstraction reaction. In the early stage of the dynamics, we find that the CN stretch mode gains energy at the expense of the energy in CH stretch mode. Published by AIP Publishing.

Item Type: Journal Article
Additional Information: Copy right for this article belong to AMER INST PHYSICS, 1305 WALT WHITMAN RD, STE 300, MELVILLE, NY 11747-4501 USA
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Depositing User: Id for Latest eprints
Date Deposited: 04 May 2018 18:48
Last Modified: 04 May 2018 18:48
URI: http://eprints.iisc.ac.in/id/eprint/59735

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