Computer simulation of some structural and spectral properties of liquid and rotator phase t-butyl chloride

Abstract

The molecular motions and interactions in liquid- and rotator-phase t-butyl chloride have been simulated numerically with a 5 × 5 site–site potential derived from Lassier and Brot. The simulated a.c.f. are compared with spectral results from infrared, far-infrared, dielectric, Raman, Rayleigh, n.m.r. and incoherent neutron-scattering spectroscopy. The simulation is more successful in reproducing single- as opposed to multi-particle correlations. The results show that the computer-simulation method is a powerful means of self-consistent analysis, given the pair potential. The effects of rotation–translation coupling are investigated in a moving frame of reference defined by the principal moment-of-inertia axes. The computer simulation shows clearly that rotation is correlated to centre-of-mass translation in both the liquid and rotator phase at 228 K. The nature of this correlation is revealed in the moving frame of reference: its effects are present in the static frame.