eprintid: 16155
rev_number: 27
userid: 1291
dir: disk0/00/01/61/55
datestamp: 2012-11-07 19:21:53
lastmod: 2021-06-12 22:55:26
status_changed: 2012-11-07 19:21:53
type: article
metadata_visibility: show
item_issues_count: 0
eprint_status: archive
creators_name: Relph, RA
creators_name: Elliott, BM
creators_name: Weddle, GH
creators_name: Johnson, MA
creators_name: Jing, D
creators_name: Jordan, KD
creators_email:
creators_email:
creators_email:
creators_email:
creators_email:
creators_email: jordan@pitt.edu
creators_id:
creators_id:
creators_id:
creators_id:
creators_id:
creators_id: JORDAN
title: Vibrationally induced interconversion of H-bonded NO 2- · H 2O isomers within NO 2- · H 2O·Ar m clusters using IR - IR pump - Probe through the OH and NO stretching vibrations
ispublished: pub
divisions: sch_as_chemistry
full_text_status: public
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 2-·H 2O 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 2-·H 2O·Ar m parent ion cluster prior to vibrational excitation and then isolate the NO 2-·H 2O·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 2-·H 2O· 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 -1; 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 -1. 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.
date: 2009-02-12
date_type: published
publication: Journal of Physical Chemistry A
volume: 113
number: 6
pagerange: 975 - 981
refereed: TRUE
issn: 1089-5639
id_number: 10.1021/jp808283r
pmid: 19152322
citation: 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 2- · H 2O isomers within NO 2- · H 2O·Ar m 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
document_url: http://d-scholarship-dev.library.pitt.edu/16155/1/licence.txt