Role of translation-rotation coupling on phase diagrams of N2-solids and related systems

Molecular solids composed of N₂-molecules are studied by Monte Carlo simulations in the constant-stress ensemble utilizing Lennard-Jones and electrostatic interactions. A phase transition was found from a high-temperature orientationally-disordered cubic phase to a low-temperature phase with Pa3 structure. The transition temperature and the jump in volume are in qualitative agreement with experimental findings. An increase in the elastic constants C₁₁ and C₄₄ and a decrease in C₁₂ at the fcc-Pa3 transition are predicted. An additional study was done by neglecting the electrostatic interaction in order to study the role of the intermolecular potential. In this case a transition to a low-temperature phase with trigonal structure was obtained. If, however, translationrotation coupling is omitted, the Lennard-Jones model exhibits the Pa3 phase too. In this study, phase transitions to hexagonal phases are suppressed by the choice of periodic boundary conditions. Many similarities are found with theoretical predicition of the translation-rotation coupling induced phase instabilities in molecular C₆₀- and C₇₀-solids.