High-resolution synchrotron FTIR spectroscopic analysis of the Coriolis interaction between the v10 = 1 and v8 = 1 states of ethylene-cis-1,2-d2

L L Ng, T L Tan, Andy Wong, Dominique R T Appadoo, Don McNaughton

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Abstract

The synchrotron Fourier transform infrared (FTIR) spectrum of the b-type ν10 band of ethylene-cis-1,2-d2 (cis-C2H2D2) was recorded at a resolution of 0.00096 cm−1 in the 550–750 cm−1 region. The measured FWHM of the lines was about 0.002 cm 1. The ν10 band, centred at 662.871885(27) cm−1 was found to be perturbed through a b-type Coriolis resonance with the infrared inactive ν8 at 759.9582(20) cm−1. In this work, 1989 infrared transitions of ν10 were assigned for the first time. These perturbed and unperturbed infrared transitions were fitted with an rms deviation of 0.00033 cm−1 using the Watson's A-reduced Hamiltonian in the Ir representation with three Coriolis terms to derive the rovibrational constants for v10 = 1 and v8 = 1 states. Ground state rovibrational constants up to two sextic terms were also derived from a fit of a total of 2532 ground state combination differences with arms deviation of 0.00030 cm−1 from the infrared transitions of the present analysis and those determined previously. The ground state constants compared favourably to the equilibrium state constants from harmonic cc-pVTZ basis set at CCSD(T), MP2 and B3LYP levels. The rotational constants of ν10 and ν8 from this work agree well with those from anharmonic calculations.

Original languageEnglish
Pages (from-to)2798-2807
Number of pages10
JournalMolecular Physics
Volume114
Issue number19
DOIs
Publication statusPublished - 1 Oct 2016

Keywords

  • cis-CHD
  • ethylene isotopologue
  • Ethylene-cis-1,2-d
  • high-resolution FTIR spectroscopy
  • rovibrational constants

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