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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Abstract
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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Details
Item Type: |
Article
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Status: |
Published |
Creators/Authors: |
Creators | Email | Pitt Username | ORCID ![](/images/orcid_id_24x24.png) |
---|
Breen, KJ | | | | Deblase, AF | | | | Guasco, TL | | | | Voora, VK | | | | Jordan, KD | jordan@pitt.edu | JORDAN | | Nagata, T | | | | Johnson, MA | | | |
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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: |
12 Jun 2021 22:55 |
URI: |
http://d-scholarship-dev.library.pitt.edu/id/eprint/16174 |
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