Raman and infrared spectra of dimethyl ether 13C-isotopologue (CH 3O 13CH 3) from a CCSD(T) potential energy surface

So far, no experimental data of the infrared and Raman spectra of 13C isotopologue of dimethyl ether are available. With the aim of providing some clues of its low-lying vibrational bands and with the hope of contributing in a next spectral analysis, a number of vibrational transition frequencies below 300 cm -1 of the infrared spectrum and around 400 cm -1 of the Raman spectrum have been predicted and their assignments were proposed. Calculations were carried out through an ab initio three dimensional potential energy surface based on a previously reported one for the most abundant dimethyl ether isotopologue (M. Villa et al., J. Phys. Chem. A 115 (2011) 13573). The potential function was vibrationally corrected and computed with a highly correlated CCSD(T) method involving the COC bending angle and the two large amplitude CH 3 internal rotation degrees of freedom. Also, the Hamiltonian parameters could represent a support for the spectral characterization of this species. Although the computed vibrational term values are expected to be very accurate, an empirical adjustment of the Hamiltonian has been performed with the purpose of anticipating some workable corrections to any possible divergence of the vibrational frequencies. Also, the symmetry breaking derived from the isotopic substitution of 13C in the dimethyl ether was taken into account when the symmetrization procedure was applied. © 2012 Elsevier Inc. All rights reserved.This work has been partially supported by European regional development funds (FEDER) under Junta de Andalucía Project P07-FQM-03014, by the Spanish Government through grants AYA2008-00446 (Plan Nacional I + D+I (2004–2007)) and FIS2011-28738-C02-02, and computing resources of CESGA.Peer Reviewe