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CCSD(T) study of CD 3-O-CD 3 and CH 3-O- CD 3 far-infrared spectra

AuthorsSenent, María Luisa ; Domínguez Gómez, R. ; Carvajal, M.; Villa, M.
Issue Date2012
PublisherAmerican Chemical Society
CitationThe journal of physical chemistry, A, Molecules, spectroscopy, kinetics, environment & general theory 116: 6901-6910 (2012)
AbstractFrom 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, 12CH 3- 16O- 12CD 3 (DME-d 3) and 12CD 3- 16O- 12CD 3 (DME-d 6), 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-d 6 belongs to the G 36 group, as the most abundant isotopologue 12CH 3- 16O- 12CH 3 (DME-h 6), while DME-d 3 is a G 18 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-d 6. 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-d 3 intensities and the band positions of the torsional overtones. © 2012 American Chemical Society.
Identifiersdoi: 10.1021/jp3030107
issn: 1089-5639
Appears in Collections:(CFMAC-IEM) Artículos
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