The effect of the Fermi resonance on the Raman scattering cross sections of the Fermi doublet ν1 and 2ν2 of liquid carbon disulfide in benzene

The effect of the Fermi resonance (FR) on the Raman scattering cross sections (RSCSs) of the Fermi doublet ν1, 2ν2 of liquid CS2 in C6H6 using the method of changing the volume concentration of the solution is investigated. We have calculated the RSCSs of the Fermi doublet ν1, 2ν2 using Onsager's theory with the 992 cm−1 Raman line of C6H6 as the internal standard. The result shows that the RSCS of the ν1 line decreases with decreasing the volume concentration of CS2, while that of the 2ν2 line unexpectedly increases. With decreasing the volume concentration of CS2, two main effects of the solvent effect (SE) and the FR in binary solution that can make the ν1, 2ν2 RSCSs change: the SE, as calculated, reduces both the ν1 and 2ν2 RSCSs; the FR plays a significant role in reducing the ν1 RSCS and enhancing the 2ν2 RSCS. In comparison with our previous investigation [J. Raman Spectrosc. 41 (2010) 776–779], it was found that the stronger the FR is, the more the RSCS of the ν1 decreases and the 2ν2 increases. Thus, we proposed that the result can be best explained by taking into account the effect of the FR on the RSCSs of the Fermi doublet. In addition, this paper also gives an explanation to the experimental results deviating from the theoretical results of the scattering coefficients of CS2 in solvent C6H6 as mentioned in Fini's paper.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► We measured the Raman Spectra of CS2 in C6H6 at different volume concentrations. ► RSCSs of Fermi doublet ν1 and 2ν2 of CS2 at different volume concentrations were calculated. ► With decreasing CS2 volume concentration, RSCSs of ν1 line decreases and 2ν2 line increases. ► We proposed that the result was mainly caused by the FR.