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Coriolis analysis of several high-resolution infrared bands of bicyclo[111]pentane-d₀ and -d₁ Public Deposited

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  • High-resolution infrared absorption spectra have been analyzed for two bicyclo[111]pentane isotopologues, C₅H₈ (-d₀) and C₅H₇D (-d₁), where in the latter the D-atom replaces a hydrogen on the C₃ symmetry axis such that the molecular symmetry is reduced from D₃ₕ to C₃ᵥ. Two (a"₂) parallel bands, v₁₇ and v₁₈, of bicyclopentane-d₀ were studied and the former was found to be profoundly affected by Coriolis coupling with the nearby (e') perpendicular band, v₁₁. Weaker coupling was observed between the v₁₈ band and the nearby v₁₃(e') band, for which fewer transitions could be assigned. For bicyclopentane-d₁, the v₅ parallel band was also studied along with the nearby v₁₅(e') band to which it is coupled through a similar type of Coriolis resonance. For both isotopologues, quantum calculations (B3LYP/cc-pVTZ) done at the anharmonic level were very helpful in unraveling the complexities caused by the Coriolis interactions, provided that care is taken in identifying the effect of any Coriolis resonances on the theoretical values of aB and q rovibrational parameters. The ground state B₀ constants were found to be 0.2399412(2) and 0.2267506(11) cm⁻¹ for the -d₀ and -d₁ isotopologues. The difference yields an Rₛ substitution value of 2.0309(2) Å for the position of the axial H atom relative to the -d₀ center of mass, a result in good accord with a corresponding Ra value of 2.044(6) Å from electron diffraction data. For both isotopologues, the theoretical results from the quantum calculations are in good agreement with all corresponding values determined from the spectra.
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  • Perry, A., Martin, M. A., Nibler, J. W., Maki, A., Weber, A., & Blake, T. A. (2012). Coriolis analysis of several high-resolution infrared bands of bicyclo[111]pentane-d0 and -d1. Journal of Molecular Spectroscopy, 276-277, 22-32. doi: 10.1016/j.jms.2012.06.008
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  • 276-277
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  • J. Nibler acknowledges the support of the Camille and HenryDreyfus Foundation in the form of a Senior Scientist Mentor Award.The research described here was performed, in part, in the EnvironmentalMolecular Sciences Laboratory, a national scientific userfacility sponsored by the Department of Energy’s Office of Biologicaland Environmental Research and located at Pacific NorthwestNational Laboratory (PNNL). PNNL is operated for the United StatesDepartment of Energy by the Battelle Memorial Institute undercontract DE-AC05-76RLO 1830.
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