Study of asymmetric wavenumber shift of the Fermi doublet ν1 − 2ν2 in the Raman spectrum of liquid carbon disulfide

The Raman spectra of liquid carbon disulfide (CS₂) diluted with benzene (C₆H₆) have been measured. By changing the CS₂, the concentration, we found an asymmetric wavenumber shift phenomenon. With decreasing concentration of CS₂, the position of the ν₁ (655 cm⁻¹) band remains practically unchanged, and the 2ν₂ (796 cm⁻¹) band shifts toward higher wavenumbers. To interpret this asymmetric wavenumber shift phenomenon of the Fermi doublet ν₁ − 2ν₂ in the Raman spectra satisfactorily, we propose a modified Bertran model. The values of the Fermi resonance (FR) parameters of CS₂ at different concentrations were calculated using the Bertran equations. In addition, we found the fundamental ν₂, which should be independent of the FR interaction, shifted to higher wavenumbers as the concentration decreased. This shift was probably driven by the tuning of the FR. Copyright © 2009 John Wiley & Sons, Ltd.