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High-resolution infrared studies of the ν10, ν11, ν14, and ν18 levels of [1.1.1]propellane Public Deposited

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  • This paper is a continuation of earlier work in which the high resolution infrared spectrum of [1.1.1]propellane was measured and its k and l structure resolved for the first time. Here we present results from an analysis of more than 16,000 transitions involving three fundamental bands v₁₀ (E' - A'₁), v₁₁ (E' - A'₁), v₁₄ (A"₂ - A'₁) and two difference bands (v₁₀–v₁₈) (E' - E") and (v₁₁ - v₁₈) (E' - E"). Additional information about v₁₈ was also obtained from the difference band (v₁₅ + v₁₈) - v₁₈ (E' - E") and the binary combination band (v₁₅ + v₁₈) (E' - A'₁). Through the use of the ground state constants reported in an earlier paper [1], rovibrational constants have been determined for all the vibrational states involved in these bands. The rovibrational parameters for the v₁₈ (E") state were obtained from combination–differences and showed no need to include interactions with other states. The v₁₀ (E') state analysis was also straight-forward, with only a weak Coriolis interaction with the levels of the v₁₄ (A"₂) state. The latter levels are much more affected by a strong Coriolis interaction with the levels of the nearby v₁₁ (E') state and also by a small but significant interaction with another state, presumably the v₁₆ (E") state, that is not directly observed. Gaussian calculations (B3LYP/cc-pVTZ) computed at the anharmonic level aided the analyses by providing initial values for many of the parameters. These theoretical results generally compare favorably with the final parameter values deduced from the spectral analyses. Finally, evidence was obtained for several level crossings between the rotational levels of the v₁₁ and v₁₄ states and, using a weak coupling term corresponding to a Δk = ±5, Δl = ∓1 matrix element, it was possible to find transitions from the ground state that, combined with transitions to the same upper state, give a value of C₀ = 0.1936515(4) cm⁻¹. This result, combined with the value of B₀ = 0.28755833(14) cm⁻¹ reported earlier [1], yields a value of 1.586277(3) Å for the length of the novel axial CC bond in propellane.
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  • Kirkpatrick, R., Masiello, T., Martin, M., Nibler, J. W., Maki, A., Weber, A., & Blake, T. A. (2012). High-resolution infrared studies of the [nu] V10, [nu] V11, [nu] V14, and [nu] V18 levels of [1.1.1]propellane. Journal of Molecular Spectroscopy, 281, 51. doi: 10.1016/j.jms.2012.09.001
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  • R. Kirkpatrick is grateful to Oregon State University for MiltonHarris, Benedict, and Shoemaker Fellowships during the course ofthis PhD thesis work [14]. J. Nibler acknowledges the support ofthe Camille and Henry Dreyfus Foundation in the form of a SeniorScientist Mentor Award. The research described here was performed,in part, in EMSL, a national scientific user facility sponsoredby the Department of Energy’s Office of Biological andEnvironmental Research and located at Pacific Northwest NationalLaboratory (PNNL). PNNL is operated for the United States Departmentof Energy by the Battelle Memorial Institute under contract DE-AC05-76RLO 1830.
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