Molecular Dynamics of the Phase Transition in Solid Deuterated Methane

Abstract

The rotational dynamics of a single deuterated methane molecule in the presence of its twelve nearest neighbours has been studied by using a computer simulation technique. The three-dimensional motion of the tetrahedral molecule is described by the appropriate algorithm equations, as well as by the well known Lennard-Jones potential. The importance of the inverse-twelfth-power repulsive potential for the dynamics of the deuterated methane molecule is also highlighted. The second-nearest neighbour interactions contribute only 7% to the potential energy of the whole system and this hardly affects the dynamics of the central molecule. A detailed analysis of the direction cosine data reveals a change in the dynamical behaviour of the molecule around the transition temperature, which could be attributed to the singularity observed in the specific heat data. Corresponding to the Lennard-Jones potential, the period of oscillation of the central molecule comes out to be 0�38xlO-12 s. Making use of the (dimensionless) average rotational kinetic energy at the transition, (ERK)critical = 6�3, and the period, the transition temperature is found to be 27�7 K, which is in quite good agreement with one of the ..\-type transition temperatures reported by Clusius et al.