Proton transfer from water to ketyl radical anion: Assessment of critical size of hydrated cluster and free energy barrier in solution from first principles simulations

Biswas, S and Dasgupta, T and Mallik, B S (2016) Proton transfer from water to ketyl radical anion: Assessment of critical size of hydrated cluster and free energy barrier in solution from first principles simulations. Chemical Physics, 477. pp. 46-51. ISSN 0301-0104

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Abstract

We present the reactivity of an organic intermediate by studying the proton transfer process from water to ketyl radical anion using gas phase electronic structure calculations and the metadynamics method based first principles molecular dynamics (FPMD) simulations. Our results indicate that during the micro solvation of anion by water molecules systematically, the presence of minimum three water molecules in the gas phase cluster is sufficient to observe the proton transfer event. The analysis of trajectories obtained from initial FPMD simulation of an aqueous solution of the anion does not show any evident of complete transfer of the proton from water. The cooperativity of water molecules and the relatively weak anion-water interaction in liquid state prohibit the full release of the proton. Using biasing potential through first principles metadynamics simulations, we report the observation of proton transfer reaction from water to ketyl radical anion with a barrier height of 16.0 kJ/mol.

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IITH Creators:
IITH CreatorsORCiD
Mallik, B Shttp://orcid.org/0000-0001-9657-1497
Item Type: Article
Uncontrolled Keywords: Proton transfer; Ketyl radical anion; First principles simulations; Metadynamics; Free energy barrier
Subjects: Chemistry
Divisions: Department of Chemistry
Depositing User: Team Library
Date Deposited: 01 Sep 2016 05:27
Last Modified: 21 Jul 2017 05:33
URI: http://raiith.iith.ac.in/id/eprint/2704
Publisher URL: https://doi.org/10.1016/j.chemphys.2016.08.022
OA policy: http://www.sherpa.ac.uk/romeo/issn/0301-0104/
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