CCSD(T) Study of CD3-O-CD3 and CH3-O-CD3 Far-Infrared Spectra

Senent Díez, María Luisa and Dominguez Gomez, Rosa and Carvajal Zaera, Miguel and Villa, M. (2012). CCSD(T) Study of CD3-O-CD3 and CH3-O-CD3 Far-Infrared Spectra. "Journal of Physical Chemistry A", v. 116 (n. 25); pp. 6901-6910. ISSN 1089-5639.


Title: CCSD(T) Study of CD3-O-CD3 and CH3-O-CD3 Far-Infrared Spectra
  • Senent Díez, María Luisa
  • Dominguez Gomez, Rosa
  • Carvajal Zaera, Miguel
  • Villa, M.
Item Type: Article
Título de Revista/Publicación: Journal of Physical Chemistry A
Date: June 2012
Volume: 116
Faculty: E.U.I.T. Obras Públicas (UPM)
Department: Ingeniería Civil: Hidráulica y Energética [hasta 2014]
Creative Commons Licenses: Recognition - No derivative works - Non commercial

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From a vibrationally corrected 3D potential energy surface determined with highly correlated ab initio calculations (CCSD(T)), the lowest vibrational energies of two dimethyl-ether isotopologues, 12CH3–16O–12CD3 (DME-d3) and 12CD3–16O–12CD3 (DME-d6), are computed variationally. The levels that can be populated at very low temperatures correspond to the COC-bending and the two methyl torsional modes. Molecular symmetry groups are used for the classification of levels and torsional splittings. DME-d6 belongs to the G36 group, as the most abundant isotopologue 12CH3–16O–12CH3 (DME-h6), while DME-d3 is a G18 species. Previous assignments of experimental Raman and far-infrared spectra are discussed from an effective Hamiltonian obtained after refining the ab initio parameters. Because a good agreement between calculated and experimental transition frequencies is reached, new assignments are proposed for various combination bands corresponding to the two deuterated isotopologues and for the 020 → 030 transition of DME-d6. Vibrationally corrected potential energy barriers, structural parameters, and anharmonic spectroscopic parameters are provided. For the 3N – 9 neglected vibrational modes, harmonic and anharmonic fundamental frequencies are obtained using second-order perturbation theory by means of CCSD and MP2 force fields. Fermi resonances between the COC-bending and the torsional modes modify DME-d3 intensities and the band positions of the torsional overtones.

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Item ID: 15800
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Deposited by: Memoria Investigacion
Deposited on: 30 Oct 2013 19:29
Last Modified: 21 Apr 2016 16:06
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