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Infrared spectroscopy of the molecular hydrogen solvated carbonium ions, CH<sup> + </sup><sub>5</sub>(H2)n (n=1–6)
The infrared spectra for the molecular hydrogen-solvated carbonium ions, CH + 5" align="middle"/>(H2)n (n=1–6) in the frequency range of 2700–4200 cm−1 are presented. Spectroscopic e...
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Kinetics of crystallizing D2O water near 150 K by Fourier transform infrared spectroscopy and a comparison with the corresponding calorimetric studies on H2O water
Crystallization kinetics of hyperquenched D2O liquid has been studied by Fourier transform infrared spectroscopy by determining the irreversible change in the spectra of stretching vibrations of the d...

Resonant ion-dip infrared spectroscopy of benzene–H2O and benzene–HOD

J. Chem. Phys. 103, 531 (1995); doi:10.1063/1.470139

Issue Date: 8 July 1995

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R. Nathaniel Pribble, Aaron W. Garrett, Kenneth Haber, and Timothy S. Zwier
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393
The Joint Institute for Laboratory Astrophysics, The University of Colorado, Boulder, Colorado 80309
Resonant ion-dip infrared spectra of C6H6–H2O and C6H6–HOD have been recorded in the OH stretch fundamental region. The spectra provide further evidence for the unique, large-amplitude motions present in these pi hydrogen-bonded complexes. In C6H6–H2O, transitions out of the lowest ortho (Pi) and para (Sigma) ground state levels are observed. A transition at 3634 cm−1 is assigned as an unresolved pair of parallel transitions (Sigma-->Sigma and Pi-->Pi) involving the symmetric stretch fundamental (at 3657 cm−1 in free H2O). In the antisymmetric stretch region, transitions at 3713, 3748, and 3774 cm−1 are assigned as Pi-->Sigma, Sigma-->Pi, and Pi-->Delta transitions, respectively. The spacing of the transitions is consistent with nearly free internal rotation of H2O about benzene's sixfold axis in both ground and vibrationally excited states. The intensities of combination bands depends critically on the mixing of some local mode character into the symmetric and antisymmetric stretches at asymmetric positions of H2O on benzene. Surprisingly, in C6H6–HOD, five transitions are observed in the OH stretch region, all arising from the ground state zero point level. Even more unusual, the higher-energy combination bands are many times stronger than the OH stretch fundamental. The local mode OH stretch has components both parallel and perpendicular to benzene's sixfold axis, leading to strong parallel and perpendicular transitions in the spectrum. A two-dimensional model involving free internal rotation and torsion of HOD in its plane is used to account for the qualitative appearance of the spectrum. The form of the OH(v=0) and OH(v=1) torsional potentials which reproduce the qualitative features of the spectrum are slightly asymmetric, double-minimum potentials with large-amplitude excursions for HOD over nearly 180°. ©1995 American Institute of Physics.
History: Received 16 February 1995; accepted 4 April 1995
Permalink: http://link.aip.org/link/?JCPSA6/103/531/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.20.Vq
    Molecular properties and interactions with photons Molecular spectra Vibrationrotation analysis
  • 33.20.Vq
    Molecular properties and interactions with photons Molecular spectra Vibrationrotation analysis
  • 34.20.Gj
    Atomic and molecular collision processes and interactions Interatomic and intermolecular potentials and forces, potential energy surfaces for collisions Intermolecular and atommolecule potentials and forces
  • YEAR: 1995

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0021-9606 (print)   1089-7690 (online)
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REFERENCES (26)
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