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No Access Submitted: 21 April 2006 Accepted: 22 August 2006 Published Online: 15 September 2006

  • Single vibronic level emission spectroscopic studies of the ground state energy levels and molecular structures of jet-cooled HGeBr, DGeBr, HGeI, and DGeI

J. Chem. Phys. 125, 114301 (2006); https://doi.org/10.1063/1.2355496
Brandon S. Tackett, Yunjing Li, and Dennis J. Clouthiera)
  • Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055
    • Kezia L. Pacheco and G. Alan Schick
  • Department of Chemistry, Eastern Kentucky University, Richmond, Kentucky 40475-3102
    • Richard H. Judge
  • Department of Chemistry, University of Wisconsin-Parkside, Kenosha, Wisconsin 53141-2000
    • more...View Affiliations
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    • Brandon S. Tackett
    • Yunjing Li
    • Dennis J. Clouthier
    • Kezia L. Pacheco
    • G. Alan Schick
    • Richard H. Judge
    ABSTRACT
    Single vibronic level dispersed fluorescence spectra of jet-cooled HGeBr, DGeBr, HGeI, and DGeI have been obtained by laser excitation of selected bands of the ÃA″1-X̃A′1 electronic transition. The measured ground state vibrational intervals were assigned and fitted to anharmonicity expressions, which allowed the harmonic frequencies to be determined for both isotopomers. In some cases, lack of a suitable range of emission data necessitated that some of the anharmonicity constants and vibrational frequencies be estimated from those of HGeCl∕DGeCl and the corresponding silylenes (HSiX). Harmonic force fields were obtained for both molecules, although only four of the six force constants could be determined. The ground state effective rotational constants and force field data were combined to calculate average (rz) and approximate equilibrium (rez) structures. For HGeBr rez(GeH)=1.593(9)Å, rez(GeBr)=2.325(21)Å, and the bond angle was fixed at our CCSD(T)/aug-cc-pVTZ ab initio value of 93.6°. For HGeI we obtained rez(GeH)=1.589(1)Å, rez(GeI)=2.525(5)Å, and bond angle=93.2°. Franck-Condon simulations of the emission spectra using ab initio Cartesian displacement coordinates reproduce the observed intensity distributions satisfactorily. The trends in structural parameters in the halogermylenes and halosilylenes can be readily understood based on the electronegativity of the halogen substituent.

    ACKNOWLEDGMENTS

    One of the authors (B.S.T.) acknowledges the support of a National Science Foundation Graduate Research Fellowship and two of the authors (G.A.S. and K.L.P.) acknowledge funding from the Kentucky NSF EPSCoR program, sponsored by both the Commonwealth of Kentucky and NSF (EPSCoR Award No. 0132295). Another author (R.H.J.) acknowledges the support of the NSF Research at Undergraduate Institutions program. This research was supported by the U.S. National Science Foundation, Grant No. CHE-0513495.

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