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Stepwise solvation enthalpies of protonated water clusters: collision-induced dissociation as an alternative to equilibrium studies

Dalleska, N. F. and Honma, Kenji and Armentrout, P. B. (1993) Stepwise solvation enthalpies of protonated water clusters: collision-induced dissociation as an alternative to equilibrium studies. Journal of the American Chemical Society, 115 (25). pp. 12125-12131. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20150622-144458490

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Abstract

Absolute reaction cross sections for interaction of H_3O^+(H_2O), (x = 1-5) with xenon are determined from thermal energies to 20 eV (CM) by using guided ion beam mass spectrometry. In all cases, the primary product is endothermic collision induced dissociation (CID) to lose one water molecule. At higher energies, additional water molecules are lost successively, indicating that evaporation is the primary pathway for dissociation. The proper interpretation of the primary CID thresholds is considered in detail and the adjustment of these values to enthalpies at standard conditions is discussed. When the effects of multiple ion-molecule collisions, internal energy of the clusters, and dissociation lifetimes are properly accounted for, we determine the following bond dissociation energies (in eV): D_0[H_3O^+-H_2O] = 1.35 ± 0.06, D_0[H_2O_2^+-H_2O] = 0.86 ± 0.06, D_0[H_7O_3^+-H_2O] = 0.71 ± 0.06, D_0[H_9O_4^+-H_2O] = 0.52 ± 0.06, and D_0[H_(11_O_5^+-H_2O] = 0.51 ± 0.08. These results are in very good agreement with enthalpies of solvation determined by equilibrium methods.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1021/ja00078a059DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00078a059PublisherArticle
ORCID:
AuthorORCID
Dalleska, N. F.0000-0002-2059-1587
Additional Information:© 1993 American Chemical Society. Received July 12, 1993. This work is supported by the National Science Foundation, Grant No. CHE 9221241. We thank the referees for several useful comments.
Funders:
Funding AgencyGrant Number
NSFCHE-9221241
Record Number:CaltechAUTHORS:20150622-144458490
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150622-144458490
Official Citation:Stepwise solvation enthalpies of protonated water clusters: collision-induced dissociation as an alternative to equilibrium studies N. F. Dalleska, Kenji Honma, and P. B. Armentrout Journal of the American Chemical Society 1993 115 (25), 12125-12131 DOI: 10.1021/ja00078a059
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58422
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:23 Jun 2015 22:48
Last Modified:11 Apr 2017 16:26

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