Study of the H−F Stretching Band in the Absorption Spectrum of (CH3)2O···HF in the Gas Phase

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 112; no. 6; pp. 1251 - 1260
• Main Authors: Bulychev, V. P, Gromova, E. I, Tokhadze, K. G
• Format: Journal Article
• Language: English
• Published: American Chemical Society 14.02.2008
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp076966f

The absorption spectra of the (CH3)2O···HF complex in the range of 4200−2800 cm-1 were recorded in the gas phase at a resolutions of 0.1 cm-1 at T = 190−340 K. The spectra obtained were used to analyze their structure and to determine the temperature dependencies of the first and second spectral moments. The band shape of the (CH3)2O···HF complex in the region of the ν1(HF) stretching mode was reconstructed nonempirically. The ν1 and ν3 stretching vibrations and four bending vibrations responsible for the formation of the band shape were considered. The equilibrium geometry and the 1D−4D potential energy surfaces were calculated at the MP2 6-311++G(2d,2p) level with the basis set superposition error taken into account. On the basis of these surfaces, a number of one- and multidimensional anharmonic vibrational problems were solved by the variational method. Solutions of auxiliary 1D and 2D vibrational problems showed the strong coupling between the modes. The energy levels, transition frequencies and intensities, and the rotational constants for the combining vibrational states necessary to reconstruct the spectrum were obtained from solutions of the 4D problem (ν1, ν3, ν5(B2), ν6(B2)) and the 2D problem (ν5(B1), ν6(B1)). The theoretical spectra reconstructed for different temperatures as a superposition of rovibrational bands associated with the fundamental, hot, sum, and difference transitions reproduce the shape and separate spectral features of the experimental spectra. The calculated value of the ν1 frequency is 3424 cm-1. Along with the frequencies and absolute intensities, the calculation yields the vibrationally averaged values of the separation between the centers of mass of the monomers Rc.-of-m., R(O···F), and r(HF) for different states. In particular, upon excitation of the ν1 mode, Rc.-of-m. becomes shorter by 0.0861 Å, and r(HF) becomes longer by 0.0474 Å.