Raman band shapes and the dynamics of liquid N2O4

The Raman spectra of the totally symmetric A _g modes, v ₁, v ₂ and v ₃, of the N₂O₄ molecule have been measured in the liquid state at 262, 279 and 297 K. The vibrational and the rotational correlation functions are calculated. The long-time exponential decay of the rotational correlation functions of all the A _g modes reflects an asymptotic diffusional behaviour of molecular reorientation. The rotational relaxation rate is found to increase with increasing temperature. A marked point of inflection from the short time inertial correlation to the long time exponential decay appears at about 0·35 ps for the v ₂ mode. This is an indication of orientational rebound arising from the librational motion in a temporary solvent cage. The isotropic bandwidth increases in the order v ₁ < v ₂ < v ₃, which is also the order of decreasing vibrational frequency. The temperature dependence of the peak frequency and of the bandwidth are also found to increase in the same order. These observations are analysed qualitatively in terms of two models of vibrational dephasing which take into account the effect of vibrational anharmonicity.