The properties of liquid nitrogen

Abstract

The light-scattering ‘anisotropy’ spectrum of liquid nitrogen has been measured for the liquid along the liquid-vapour coexistence line from 69·4 K (almost the triple point) to near the critical point at 125 K and for the gas under pressure at 128 K. The spectrum is very broad (HWHH∼50 cm^-1) due to rapid molecular reorientation. The molecular anisotropy spectrum is approximately gaussian, corresponding to a correlation time for molecular reorientation of order 2 × 10^-13 s at 80 K which is comparable with that obtained from nuclear magnetic resonance. A gaussian rather than a lorentzian form arises because molecular reorientation is not a ‘slow’ variable. Above the critical temperature the molecular anisotropy spectrum can be roughly described as a collision-broadened rotational line spectrum. The spectrum and its time Fourier Transform are analysed in terms of the dynamical correlation of orientation of the molecules. A component of the spectrum due to induced polarization is separated from the anisotropy contribution by a study of the far wing of the spectrum and is observed on the Stokes side out to about 250 cm^-1. This depends exponentially on frequency shift and is interpreted in terms of molecular collision dynamics. The correlation time for this motion is about a factor three shorter than that for molecular reorientation. The spectra are markedly asymmetric after all experimental corrections for asymmetry have been made. The asymmetry is shown to correspond to the detailed balance factor. It is pointed out that this factor should be allowed for in the case of induced scattering, in particular. A theoretical analysis is given of the effect of correlation of molecular orientation on the light-scattering spectrum for centrosymmetric linear molecules. In particular it is shown that the normalized second moment of the spectrum is unaffected by correlation of orientation.