Add time:09/24/2019         Source:sciencedirect.com

Raman spectra of XeF4 and XeF6 in the nonaqueous HF solutions at various concentrations and vibrational spectra of the [XeF5]+ cation in the solid state and in the HF solutions over a wide range of vibrational frequencies have been studied. The assignments of the observed vibrational bands of the [XeF5]+ cation and XeF6-HF system has been made. A number of associates or solvates being formed as a result of the donor–acceptor interaction between Lewis base and Lewis acid has been shown to exist alongside with ionized monomeric and polymeric modifications of XeF6 in the HF solution such as ([XeF5]+F−)n (n=1, 2, 4). The contours of the ν1(A1g) band of XeF4 with frequency 552 cm−1 and bands of stretching modes of ([XeF5]+F−)n (n=1, 2, 4) with frequency in the range of 600–670 cm−1 are analysed. The correlation functions of the vibrational and rotational relaxation as well as the corresponding characteristic time for these processes have been calculated. A conclusion has been driven at that it is vibrational dephasing that makes the major contribution to the formation of ([XeF5]+F)4 and ([XeF5]+F−)2 band contours, while in the case of [XeF5]+F− and XeF4 the contributions of vibrational dephasing and rotational relaxation nearly coincide.

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