A theoretical investigation of the temperature dependence of the optical Kerr effect and Raman spectroscopy of liquid CS2

The ambient pressure, temperature dependent optical Kerr effect (OKE) spect ral density of CS2 has been calculated by way of time correlation function (TCF) and instantaneous normal mode (INM) methods and compared with corresp onding experimental OKE data [R. A. Farrer, B. J. Loughnane, L. A. Deschene s, and J. T. Fourkas, J. Chem. Phys. 106, 6901 (1997)]. Over this temperatu re range the viscosity of CS2 varies by more than a factor of 5, and the mo lecular dynamics (MD) spectroscopic methods employed do an excellent job in capturing the associated changes in molecular motions that lead to the obs erved spectroscopy. The resulting TCF spectra are also in very good agreeme nt with experimental measurements at all temperatures, and this is remarkab le considering the range of conditions considered. When compared in the red uced Raman spectrum form, where the INM spectral density is proportional to the squared polarizability derivative weighted density of states (DOS), th e INM results agree very well with the TCF results, and the low frequency O KE feature corresponding to rotational reorientation is suppressed in this form. Interestingly, the INM signal includes a significant contribution fro m the imaginary INM's at all the temperatures considered, and these contrib utions are crucial to the agreement between INM and TCF results. Furthermor e, the INM approximation to the signal (OKE or reduced Raman) demonstrates that the contribution (spectral density) of the real INM's remains nearly u nchanged over the temperature range considered, while the imaginary contrib ution grows with increasing temperature. The signal from the imaginary INM' s is therefore deduced to be responsible for a large part of the temperatur e dependence of the OKE spectral density. Finally, the molecular motions th at contribute to the OKE signal are analyzed using INM methods. (C) 2000 Am erican Institute of Physics. [S0021-9606(00)51043-5].