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Exploring the correlation between network structure and electron binding energy in the (H2 O) 7- cluster through isomer-photoselected vibrational predissociation spectroscopy and ab initio calculations: Addressing complexity beyond types I-III

Roscioli, JR and Hammer, NI and Johnson, MA and Diri, K and Jordan, KD (2008) Exploring the correlation between network structure and electron binding energy in the (H2 O) 7- cluster through isomer-photoselected vibrational predissociation spectroscopy and ab initio calculations: Addressing complexity beyond types I-III. Journal of Chemical Physics, 128 (10). ISSN 0021-9606

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Abstract

We report a combined photoelectron and vibrational spectroscopy study of the (H2 O) 7- cluster anions in order to correlate structural changes with the observed differences in electron binding energies of the various isomers. Photoelectron spectra of the (H2 O) 7- Arm clusters are obtained over the range of m=0-10. These spectra reveal the formation of a new isomer (I′) for m<5, the electron binding energy of which is about 0.15 eV higher than that of the type I form previously reported to be the highest binding energy species [Coe, J. Chem. Phys. 92, 3980 (1990)]. Isomer-selective vibrational predissociation spectra are obtained using both the Ar dependence of the isomer distribution and photochemical depopulation of the more weakly (electron) binding isomers. The likely structures of the isomers at play are identified with the aid of electronic structure calculations, and the electron binding energies, as well as harmonic vibrational spectra, are calculated for 28 low-lying forms for comparison with the experimental results. The HOH bending spectrum of the low binding type II form is dominated by a band that is moderately redshifted relative to the bending origin of the bare water molecule. Calculations trace this feature primarily to the bending vibration localized on a water molecule in which a dangling H atom points toward the electron cloud. Both higher binding forms (I and I′) display the characteristic patterns in the bending and OH stretching regions signaling electron attachment primarily to a water molecule in an AA binding site, a persistent motif found in non-isomer-selective spectra of the clusters up to (H2 O) 50-. © 2008 American Institute of Physics.

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Details

Item Type: Article
Status: Published
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Roscioli, JR
Hammer, NI
Johnson, MA
Diri, K
Jordan, KDjordan@pitt.eduJORDAN
Date: 25 March 2008
Date Type: Publication
Journal or Publication Title: Journal of Chemical Physics
Volume: 128
Number: 10
DOI or Unique Handle: 10.1063/1.2827475
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0021-9606
PubMed ID: 18345895
Date Deposited: 07 Nov 2012 19:27
Last Modified: 02 Feb 2019 15:56
URI: http://d-scholarship-dev.library.pitt.edu/id/eprint/16148

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