Molecular dynamics of a plastic crystal with two types of orientational disorder: Static and dynamic properties of plastic bicyclooctane

A molecular dynamics simulation of a realistic model of bicyclo-octane [HC(CH₂-CH₂)₃CH] in its plastic phase has been performed at three different temperatures. The interactions between the molecules of the simulated system are calculated with phenomenological exp-6 additive atom-atom potentials. The molecules are considered rigid and their equations of motion are integrated using a method of constraints. A special attention is given to the problem of the C-H bond value. The static analysis of the molecular dynamics (MD) results yields a clear description of two types of orientational order: It confirms the experimental results about the equipartition of the molecular threefold axes around the eight 〈111〉 crystallographic axes and it furthermore unambiguously shows the existence of six preferred orientations for the orientational order of the molecules around their threefold axes where a previous experimental work concluded in favor of a quasifree rotation. The mean-square displacement amplitudes of the molecular centers of mass reveal that our simulation model is not impeded by the abnormal behavior of the exp-6 potentials at small interactive distances. From a dynamical point of view, the molecular dynamics scheme clearly shows that the jumps are not instantaneous and are slightly more diverse than previously assumed. In order to achieve a precise description of these jumps, we propose to make a conceptual distinction between the mean residence times and the correlation times. By contrast with a former MD simulation, our model gives two sets of distinct characteristic times which perfectly agree with the experimentally deduced values. Given the simplifying assumptions entering the experimental models, the quality of this latter agreement also shows a certain lack of sensitivity vis à vis the exact nature of the underlying microscopic mechanisms. We also examined the ability of our model to simulate the behavior of a monovacancy. We found the influence of such a defect on its immediate neighborhood to be very small even when considering the nature of the complex orientational (dis)order.