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  Thermodynamics of Water Dimer Dissociation in the Primary Hydration Shell of the Iodide Ion with Temperature-Dependent Vibrational Predissociation Spectroscopy

Wolke, C. T., Menges, F. S., Toetsch, N., Gorlova, O., Fournier, J. A., Weddle, G. H., et al. (2015). Thermodynamics of Water Dimer Dissociation in the Primary Hydration Shell of the Iodide Ion with Temperature-Dependent Vibrational Predissociation Spectroscopy. The Journal of Physical Chemistry A, 119(10), 1859-1866. doi:10.1021/jp510250n.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0026-C1E2-C Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0026-C1E3-A
Genre: Journal Article

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 Creators:
Wolke, Conrad T.1, Author
Menges, Fabian S.1, Author
Toetsch, Niklas2, Author
Gorlova, Olga1, Author
Fournier, Joseph A.1, Author
Weddle, Gary H.3, Author
Johnson, Mark A.1, Author
Heine, Nadja4, Author              
Esser, Tim4, Author              
Knorke, Harald4, Author              
Asmis, Knut R.5, Author              
McCoy, Anne B.6, Author
Arismendi-Arrieta, Daniel J.7, 8, Author
Prosmiti, Rita7, Author
Paesani, Francesco8, Author
Affiliations:
1Sterling Chemistry Laboratory, Yale University, New Haven, Connecticut 06525, United States, ou_persistent22              
2Graduate School of Chemistry and Biochemistry, Ruhr-Universität Bochum, Universitätsstraße 150, D-44801 Bochum, Germany, ou_persistent22              
3Department of Chemistry, Fairfield University, Fairfield, Connecticut 06824, United States, ou_persistent22              
4Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              
5Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, ou_persistent22              
6Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States, ou_persistent22              
7Instituto de Fıś ica Fundamental (IFF-CSIC), CSIC, Serrano 123, 28006 Madrid, Spain, ou_persistent22              
8Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States, ou_persistent22              

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 Abstract: The strong temperature dependence of the I·(H2O)2 vibrational predissociation spectrum is traced to the intracluster dissociation of the ion-bound water dimer into independent water monomers that remain tethered to the ion. The thermodynamics of this process is determined using van’t Hoff analysis of key features that quantify the relative populations of Hbonded and independent water molecules. The dissociation enthalpy of the isolated water dimer is thus observed to be reduced by roughly a factor of three upon attachment to the ion. The cause of this reduction is explored with electronic structure calculations of the potential energy profile for dissociation of the dimer, which suggest that both reduction of the intrinsic binding energy and vibrational zero-point effects act to weaken the intermolecular interaction between the water molecules in the first hydration shell. Additional insights are obtained by analyzing how classical trajectories of the I·(H2O)2 system sample the extended potential energy surface with increasing temperature.

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Language(s): eng - English
 Dates: 2015-01-022014-10-102015-02-032015-02-032015-03-12
 Publication Status: Published in print
 Pages: 8
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1021/jp510250n
 Degree: -

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Title: The Journal of Physical Chemistry A
  Other : J. Phys. Chem. A
Source Genre: Journal
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Publ. Info: Columbus, OH : American Chemical Society
Pages: - Volume / Issue: 119 (10) Sequence Number: - Start / End Page: 1859 - 1866 Identifier: ISSN: 1089-5639
CoNE: /journals/resource/954926947766_4