CCSD(T) Study of Dimethyl-Ether Infrared and Raman Spectra

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 115; no. 46; pp. 13573 - 13580
• Main Authors: Villa, M, Senent, M. L, Dominguez-Gomez, R, Alvarez-Bajo, O, Carvajal, M
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 24.11.2011
• Subjects: A: Molecular Structure, Quantum Chemistry, General Theory; Accuracy; Anharmonicity; Bands; Bending; Computation; Mathematical analysis; Methyl Ethers - chemistry; Quantum Theory; Spectrophotometry, Infrared; Spectroscopy; Spectrum Analysis, Raman; Three dimensional
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp2062223

CCSD(T) state-of-the-art ab initio calculations are used to determine a vibrationally corrected three-dimensional potential energy surface of dimethyl-ether depending on the two methyl torsions and the COC bending angle. The surface is employed to obtain variationally the lowest vibrational energies that can be populated at very low temperatures. The interactions between the bending and the torsional coordinates are responsible for the displacements of the torsional overtone bands and several combination bands. The effect of these interactions on the potential parameters is analyzed. Second order perturbation theory is used as a help for the understanding of many spectroscopic parameters and to obtain anharmonic fundamentals for the 3N – 9 neglected modes as well as the rotational parameters. To evaluate the surface accuracy and to verify previous assignments, the calculated vibrational levels are compared with experimental data corresponding to the most abundant isotopologue. The surface has been empirically adjusted for understanding the origin of small divergences between ab initio calculations and experimental data. Our calculations confirm previous assignments and show the importance of including the COC bending degree of freedom for computing with a higher accuracy the excited torsional term values through the Fermi interaction. Besides, this work shows a possible lack of accuracy of some available experimental transition frequencies and proposes a new assignment for a transition line. As an example, the transition 100 → 120 has been computed at 445.93 cm–1, which is consistent with the observed transition frequency in the Raman spectrum at 450.5 cm–1.