Structure of hydrogen fluoride complexes with diethylketone in a HF–Et2CO solution

详细

The optimal configurations and the vibrational spectra of heteroassociates (HAs) of hydrogen fluoride and diethylketone molecules with 1:1, 2:2, 4:1, and 8:2 compositions are calculated using the density functional theory (B3LYP/6-31++G(d,p)). A comparison of the results of calculations and the known experimental data reveal that the following stable hydrogen-bonded molecular complexes are formed in HF–Et₂CO solutions: the C_2h symmetry cyclic heterotetramer (HF)₂∙(Et₂CO)₂ and the tricyclic HA (HF)₈∙(Et₂CO)₂ formed based on the heterotetramer by the binding of two (HF)₃ moieties. It is shown that it is appropriate to decompose the spectral curve into the Gaussian functions or the Lorentzian functions to determine the frequencies and the integrated intensities of broad and overlapped IR bands. The first type of the decomposition enables one to estimate more correctly the values of the band frequencies, and the second type makes it possible to find more correctly the band intensities.