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Title: Accurate first-principles calculations for {sup 12}CH{sub 3}D infrared spectra from isotopic and symmetry transformations

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4890956· OSTI ID:22419944
;  [1];  [2]
  1. Groupe de Spectrométrie Moléculaire et Atmosphérique, UMR CNRS 6089, BP 1039, F-51687, Reims Cedex 2 (France)
  2. Laboratory of Theoretical Spectroscopy, Institute of Atmospheric Optics, SB RAS, 634055 Tomsk (Russian Federation)

Accurate variational high-resolution spectra calculations in the range 0-8000 cm{sup −1} are reported for the first time for the monodeutered methane ({sup 12}CH{sub 3}D). Global calculations were performed by using recent ab initio surfaces for line positions and line intensities derived from the main isotopologue {sup 12}CH{sub 4}. Calculation of excited vibrational levels and high-J rovibrational states is described by using the normal mode Eckart-Watson Hamiltonian combined with irreducible tensor formalism and appropriate numerical procedures for solving the quantum nuclear motion problem. The isotopic H→D substitution is studied in details by means of symmetry and nonlinear normal mode coordinate transformations. Theoretical spectra predictions are given up to J = 25 and compared with the HITRAN 2012 database representing a compilation of line lists derived from analyses of experimental spectra. The results are in very good agreement with available empirical data suggesting that a large number of yet unassigned lines in observed spectra could be identified and modeled using the present approach.

OSTI ID:
22419944
Journal Information:
Journal of Chemical Physics, Vol. 141, Issue 4; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
Country of Publication:
United States
Language:
English