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Title: Theoretical rotation-vibration spectrum of thioformaldehyde

We present a variational calculation of the first comprehensive T = 300 K rovibrational line list for thioformaldehyde, H{sub 2}CS. It covers 41 809 rovibrational levels for states up to J{sub max} = 30 with vibrational band origins up to 5000 cm{sup −1} and provides the energies and line intensities for 547 926 transitions from the ground vibrational state to these levels. It is based on our previously reported accurate ab initio potential energy surface and a newly calculated ab initio dipole moment surface. Minor empirical adjustments are made to the ab initio equilibrium geometry to reduce systematic errors in the predicted intra-band rotational energy levels. The rovibrational energy levels and transition intensities are computed variationally by using the methods implemented in the computer program TROVE. Transition wavelengths and intensities are found to be in excellent agreement with the available experimental data. The present calculations correctly reproduce the observed resonance effects, such as intensity borrowing, thus reflecting the high accuracy of the underlying ab initio surfaces. We report a detailed analysis of several vibrational bands, especially those complicated by strong Coriolis coupling, to facilitate future laboratory assignments.
Authors:
 [1] ; ;  [2]
  1. Department of Physics and Astronomy, University College London, London, WC1E 6BT (United Kingdom)
  2. Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D–45470 Mülheim an der Ruhr (Germany)
Publication Date:
OSTI Identifier:
22251336
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 20; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; COUPLING; DIPOLE MOMENTS; ROTATION; SPECTRA; SURFACES; VIBRATIONAL STATES; WAVELENGTHS