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Isolating the spectral signatures of individual sites in water networks using vibrational double-resonance spectroscopy of cluster isotopomers

Guasco, TL and Elliott, BM and Johnson, MA and Ding, J and Jordan, KD (2010) Isolating the spectral signatures of individual sites in water networks using vibrational double-resonance spectroscopy of cluster isotopomers. Journal of Physical Chemistry Letters, 1 (15). 2396 - 2401.

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Abstract

We report the spectral signatures of water molecules occupying individual sites in an extended H-bonding network using mass-selective, double-resonance vibrational spectroscopy of isotopomers. The scheme is demonstrated on the water heptamer anion, (H2O)7̄ where we first randomly incorporate a single, intact D2O molecule to create an ensemble of isotopomers. The correlation between the two OD stretching frequencies and that of the intramolecular DOD bending transition is then revealed by photochemical modulation of the isotopomer population responsible for particular features in the vibrational spectrum. The observed patterns confirm the assignment of the dominant doublet, appearing most red-shifted from the free OD stretch, to a single water molecule attached to the network in a double H-bond acceptor (AA) arrangement. The data also reveal the unanticipated role of accidentally overlapping transitions, where the highest-energy OD stretch, for example, occurs with its companion OD stretch obscured by the much stronger AA feature. © 2010 American Chemical Society.


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Details

Item Type: Article
Status: Published
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Guasco, TL
Elliott, BM
Johnson, MA
Ding, J
Jordan, KDjordan@pitt.eduJORDAN
Date: 5 August 2010
Date Type: Publication
Journal or Publication Title: Journal of Physical Chemistry Letters
Volume: 1
Number: 15
Page Range: 2396 - 2401
DOI or Unique Handle: 10.1021/jz100730q
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
Date Deposited: 30 Apr 2013 20:54
Last Modified: 22 Jun 2021 12:55
URI: http://d-scholarship.pitt.edu/id/eprint/18422

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