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Bottom-up view of water network-mediated CO <inf>2</inf> reduction using cryogenic cluster ion spectroscopy and direct dynamics simulations

Breen, KJ and Deblase, AF and Guasco, TL and Voora, VK and Jordan, KD and Nagata, T and Johnson, MA (2012) Bottom-up view of water network-mediated CO <inf>2</inf> reduction using cryogenic cluster ion spectroscopy and direct dynamics simulations. Journal of Physical Chemistry A, 116 (3). 903 - 912. ISSN 1089-5639

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The transition states of a chemical reaction in solution are generally accessed through exchange of thermal energy between the solvent and the reactants. As such, an ensemble of reacting systems approaches the transition state configuration of reactant and surrounding solvent in an incoherent manner that does not lend itself to direct experimental observation. Here we describe how gas-phase cluster chemistry can provide a detailed picture of the microscopic mechanics at play when a network of six water molecules mediates the trapping of a highly reactive "hydrated electron" onto a neutral CO 2 molecule to form a radical anion. The exothermic reaction is triggered from a metastable intermediate by selective excitation of either the reactant CO 2 or the water network, which is evidenced by the evaporative decomposition of the product cluster. Ab initio molecular dynamics simulations of energized CO 2•(H 2O) 6- clusters are used to elucidate the nature of the network deformations that mediate intracluster electron capture, thus revealing the detailed solvent fluctuations implicit in the Marcus theory for electron-transfer kinetics in solution. © 2011 American Chemical Society.


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Item Type: Article
Status: Published
CreatorsEmailPitt UsernameORCID
Breen, KJ
Deblase, AF
Guasco, TL
Voora, VK
Jordan, KDjordan@pitt.eduJORDAN
Nagata, T
Johnson, MA
Date: 26 January 2012
Date Type: Publication
Journal or Publication Title: Journal of Physical Chemistry A
Volume: 116
Number: 3
Page Range: 903 - 912
DOI or Unique Handle: 10.1021/jp209493v
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 1089-5639
MeSH Headings: Carbon Dioxide--chemistry; Kinetics; Molecular Dynamics Simulation; Oxidation-Reduction; Spectrum Analysis; Water--chemistry
PubMed ID: 22145700
Date Deposited: 12 Nov 2012 14:54
Last Modified: 22 Jun 2021 12:55


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