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Vibrationally induced interconversion of H-bonded NO <inf>2</inf><sup>-</sup> · H <inf>2</inf>O isomers within NO <inf>2</inf><sup>-</sup> · H <inf>2</inf>O·Ar <inf>m</inf> clusters using IR - IR pump - Probe through the OH and NO stretching vibrations

Relph, RA and Elliott, BM and Weddle, GH and Johnson, MA and Jing, D and Jordan, KD (2009) Vibrationally induced interconversion of H-bonded NO <inf>2</inf><sup>-</sup> · H <inf>2</inf>O isomers within NO <inf>2</inf><sup>-</sup> · H <inf>2</inf>O·Ar <inf>m</inf> clusters using IR - IR pump - Probe through the OH and NO stretching vibrations. Journal of Physical Chemistry A, 113 (6). 975 - 981. ISSN 1089-5639

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Abstract

We introduce a method based on sequential application of vibrational predissociation spectroscopy to explore the high-amplitude rearrangements available in a small H-bonded complex that is vibrationally excited within a larger Ar cluster. The weakly bound Ar atoms play the role of a solvent in mediating the energy content of the embedded system, ultimately quenching it into local minima through evaporation. We demonstrate the approach on the NO ·H O binary hydrate, which is known to occur in two nearly isoenergetic isomeric forms. The scheme involves three stages of mass separation to select a particular NO ·H O·Ar parent ion cluster prior to vibrational excitation and then isolate the NO ·H O·Ar fragment ions for interrogation using resonant vibrational predissociation with a second infrared laser. The initial vibrational excitation selectively energizes one of the isomers through one of its characteristic resonances while the predissociation spectrum of the NO ·H O· Ar fragment encodes the distribution of isomers present after Ar evaporation. Isomerization from the front- to backside form is found to occur upon excitation of the NO stretch near 1200 cm ; although the reverse reaction is not observed upon excitation of the NO stretch, it is observed upon excitation of the higher-energy OH stretching fundamental near 3000 cm . We discuss these observations in the context of the calculated isomerization energetics, which focus on the minimum energy structures for the isomers as well as the transition states for their interconversion. © 2009 American Chemical Society. 2 2 2 2 m 2 2 2 2 - - - - -1 -1


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Details

Item Type: Article
Status: Published
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Relph, RA
Elliott, BM
Weddle, GH
Johnson, MA
Jing, D
Jordan, KDjordan@pitt.eduJORDAN
Date: 12 February 2009
Date Type: Publication
Journal or Publication Title: Journal of Physical Chemistry A
Volume: 113
Number: 6
Page Range: 975 - 981
DOI or Unique Handle: 10.1021/jp808283r
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 1089-5639
PubMed ID: 19152322
Date Deposited: 07 Nov 2012 19:21
Last Modified: 30 Mar 2021 12:55
URI: http://d-scholarship.pitt.edu/id/eprint/16155

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