High-Resolution Infrared Studies of Perdeutero-Spiropentane, C₅D₈

Journal Article · Tue May 17 00:00:00 EDT 2016 · Journal of Molecular Spectroscopy

DOI:https://doi.org/10.1016/j.jms.2016.05.003· OSTI ID:1322496

Erickson, Blake A. ^[1]; Ju, X. ^[1]; Nibler, Joseph W. ^[1]; Beaudry, Chris M. ^[1]; Blake, Thomas A. ^[2]

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1. Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry
2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Perdeutero-spiropentane (C₅D₈) has been synthesized and infrared and Raman spectra are reported for the first time. Wavenumber assignments are made for most of the fundamental vibrational modes. Gas phase infrared spectra were recorded at a resolution (0.002 cm^-1) sufficient to resolve individual rovibrational lines and show evidence of strong Coriolis and/or Fermi resonance interactions for most bands. However a detailed rovibrational analysis of the fundamental v₁₅ (b₂) parallel band proved possible and a fit of more than 1600 lines yielded a band origin of 1053.84465(10) cm^-1 and ground state constants (in units of cm^-1): B₀ = 0.1120700(9), D_J = 1.51(3) x10^-8, D_JK = 3.42(15) x10^-8. We note that the B₀ value is significantly less than a value of Ba = 0.1140 cm-1 calculated using structural parameters from an earlier electron diffraction (ED) study, whereas one expects B_a to be lower than B₀ because of thermal averaging over higher vibrational levels. A similar discrepancy was noted in an earlier study of C₅H₈ [1]. The structural and spectroscopic results are in good accord with values computed at the anharmonic level using the B3LYP density functional method with a cc-pVTZ basis set.

• Research Organization: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1322496
• Report Number(s): PNNL-SA-118043
• Journal Information: Journal of Molecular Spectroscopy, Vol. 325; ISSN 0022-2852
• Publisher: Elsevier
• Country of Publication: United States
• Language: English

Related Subjects

Spiropentane
C5H8 and C5D8
High-resolution infrared spectrum
Rovibrational constants
Molecular structure: DFT study