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Experimental and theoretical study of the infrared spectra of BrHI– and BrDI–

J. Chem. Phys. 121, 7259 (2004); doi:10.1063/1.1794671

Issue Date: 15 October 2004

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M. J. Nee, A. Osterwalder, and D. M. Neumark
Department of Chemistry, University of California, Berkeley, California 94720
Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 94720

C. Kaposta and C. Cibrián Uhalte
Institut für Experimentalphysik, Freie Universität Berlin, Arnimallee 14, 14195 Berlin, Germany

T. Xie, A. Kaledin, and J. M. Bowman
Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322

S. Carter
Department of Chemistry, University of Reading, Reading, United Kingdom

K. R. Asmis
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
Gas phase vibrational spectra of BrHI– and BrDI– have been measured from 6 to 17 µm (590–1666 cm–1) using tunable infrared radiation from the free electron laser for infrared experiments in order to characterize the strong hydrogen bond in these species. BrHI–·Ar and BrDI–·Ar complexes were produced and mass selected, and the depletion of their signal due to vibrational predissociation was monitored as a function of photon energy. Additionally, BrHI– and BrDI– were dissociated into HBr (DBr) and I– via resonant infrared multiphoton dissociation. The spectra show numerous transitions, which had not been observed by previous matrix studies. New ab initio calculations of the potential-energy surface and the dipole moment are presented and are used in variational ro-vibrational calculations to assign the spectral features. These calculations highlight the importance of basis set in the simulation of heavy atoms such as iodine. Further, they demonstrate extensive mode mixing between the bend and the H-atom stretch modes in BrHI– and BrDI– due to Fermi resonances. These interactions result in major deviations from simple harmonic estimates of the vibrational energies. As a result of this new analysis, previous matrix-isolation spectra assignments are reevaluated. ©2004 American Institute of Physics.
History: Received 19 July 2004; accepted 27 July 2004
Permalink: http://link.aip.org/link/?JCPSA6/121/7259/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.20.Ea
    Infrared molecular spectra
  • 33.80.Gj
    Diffuse molecular spectra; predissociation, photodissociation
  • 31.15.Ar
    Ab initio calculations (atoms and molecules)
  • 33.20.Vq
    Vibration-rotation analysis (molecular spectra)
  • 33.80.Rv
    Multiphoton ionization and excitation to highly excited states in molecules e.g., Rydberg states
  • 33.15.Fm
    Molecular bond strengths, dissociation energies
  • 31.50.Df
    Potential energy surfaces for excited electronic states (atoms and molecules)
  • YEAR: 2004

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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