Cooperative motion in liquids: On librational dynamics of chloroform throughout its normal liquid-phase range

This is the authors' abstract. We don't add key points for this paper.

We have extended the Raman spectral accumulations of the ν3 mode (A1, 367 cm−1) of liquid CHCl3–Cl-35 and its simulation in terms of an orientational equilibrium renewal process [W. G. Rothschild, R. M. Cavagnat, and P. Maraval, J. Chem. Phys. 99, 8922 (1993)] to a temperature of 338 K, about the normal boiling point of the system (335 K). The values of the best-fit parameters predict that the orientational motion of liquid chloroform, even at such a relatively high kinetic energy, is described predominantly by libratory states; their lifetime (∼1 ps) is four times longer than that of the free-rotational steps. The character of the orientational motion of the system, when traversing the range of 213 to 338 K from just above its melting to near its boiling point at about atmospheric pressure, reflects the softening of the liquid-cage structure in terms of an increasing dispersion and/or a decreasing value of the mean libration frequency, a lowering of the depth of its potential well, but near-invariance of its lifetime. Simultaneously, there is an approximately twofold increase in the lifetime of the much shorter stages of free-rotational motion. In essence, the system dynamics remain that of an assembly of librators.