Rotationally resolved infrared spectroscopy of adamantane

• Published in: The Journal of chemical physics 2012-01, Vol.136 (2), p.024310-024310-12
• Main Authors: Pirali, O., Boudon, V., Oomens, J., Vervloet, M.
• Format: Article
• Language: English
• Subjects: Adamantane - chemistry; Quantum Theory; Rotation; Software; Spectrophotometry, Infrared
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.3666853

We present the first rotationally resolved spectra of adamantane (C 10 H 16 ) applying gas-phase Fourier transform infrared (IR) absorption spectroscopy. High-resolution IR spectra are recorded in the 33-4500 cm −1 range using as source of IR radiation both synchrotron radiation (at the AILES beamline of the SOLEIL synchrotron) as well as a classical globar. Adamantane is a spherical top molecule with tetrahedral symmetry ( T d point group) and has no permanent dipole moment in its vibronic ground state. Of the 72 fundamental vibrational modes in adamantane, only 11 are IR active. Here we present rotationally resolved spectra for seven of them: ν 30 , ν 28 , ν 27 , ν 26 , ν 25 , ν 24 , and ν 23 . The typical rotational structure of spherical tops is observed and analyzed using the STDS software developed in the Dijon group, which provides the first accurate energy levels and rotational constants for seven fundamental modes. Rotational levels with quantum numbers as high as J = 107 have been identified and included in the fit leading to a typical standard deviation of about 10 −3 cm −1 .