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  Vibrational Spectroscopy of the Water-Nitrate Complex in the OH Stretching Region

Heine, N., Kratz, E., Bergmann, R., Schofield, D., Asmis, K. R., Jordan, K., et al. (2014). Vibrational Spectroscopy of the Water-Nitrate Complex in the OH Stretching Region. The Journal of Physical Chemistry A, 118(37), 8188-8197. doi:10.1021/jp500964j.

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 Creators:
Heine, Nadja1, Author              
Kratz, E.2, Author
Bergmann, Risshu1, Author              
Schofield, D.3, Author
Asmis, Knut R.1, 4, Author              
Jordan, K.D.2, Author
McCoy, A.B.5, Author
Affiliations:
1Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              
2Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, ou_persistent22              
3Department of Chemistry and Biochemistry, Seattle Pacic University, Seattle, WA 98119, ou_persistent22              
4Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstrasse 2, D-04103 Leipzig, Germany, ou_persistent22              
5Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, ou_persistent22              

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Free keywords: Infrared, photodissociation, anharmonic, Hydrogen-bond
 Abstract: The vibrational spectroscopy of the nitrate-water isotopologues is studied in the O-H and O-D stretching regions using temperature-dependent infrared multiple photon dissociation spectroscopy combined with anharmonic electronic structure calculations. At a temperature of 15 K a series of discrete peaks is observed in the IRMPD spectra of [(NO3-)(H2O)], [(NO3-)(HDO)] and [(NO3-)(D2O)]. This structure is considerably more complex than predicted by harmonic calculations. Signal is only observed in the hydrogen-bonded O-H (O-D) stretching region, characteristic of a double hydrogen-bond donor binding motif. With increasing temperature the peaks broaden, leading to a quasi-continuous absorption from 3150-3600 cm-1 (2300-2700 cm-1) for [(NO3-)(H2O)] ([(NO3-)(D2O)]) and, above 100 K, an additional band in the free O-H (O-D) stretching region, suggesting the population of complexes containing only a single hydrogen-bond at higher internal energies. Vibrational configuration interaction calculations confirm that much of the structure observed in the IRMPD spectra derives from progressions in the water rock resulting from strong cubic coupling between the O-H (O-D) stretch and water rock degrees of freedom. The spectra of both [(NO3-)(H2O)] and [(NO3-)(D2O)] display a strong peak that does not derive from the water rock progression but results instead from a Fermi resonance between the O-H (O-D) stretch and H-O-H (D-O-D) bend overtone. Additional insight into the nature of the O-H (O-D) stretch and water rocking coupling in these complexes is provided by an effective Hamiltonian that allows for the cubic coupling between the O-H stretch and water rock degrees of freedom.

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Language(s): eng - English
 Dates: 2014-01-272014-032014-04-032014-09-18
 Publication Status: Published in print
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jp500964j
 Degree: -

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Title: The Journal of Physical Chemistry A
  Other : J. Phys. Chem. A
Source Genre: Journal
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Publ. Info: Columbus, OH : American Chemical Society
Pages: - Volume / Issue: 118 (37) Sequence Number: - Start / End Page: 8188 - 8197 Identifier: ISSN: 1089-5639
CoNE: https://pure.mpg.de/cone/journals/resource/954926947766_4