Reorientational motion in binary mixtures: molecular dynamics simulations

Molecular reorientational motion has been studied in a dilute solution of linear ‘tracer’ molecules in a solvent that exhibits liquid, plastic and crystalline phases. Molecular dynamics simulations have been used to extract reorientational correlation functions for both solvent and solute species as functions of temperature in all phases. The transition from the liquid to the plastic phase (upon cooling) results in less hindered tracer rotation, as evidenced by the more rapid decay of orientational correlation. These surprising dynamics are interpreted in terms of structural changes at freezing that lead to a less confining local tracer environment. The findings support a recent experimental result obtained from polarized Raman scattering on a solution of CS2 tracers in a cyclohexane host.