Molecular crystal global phase diagrams. I. Method of construction

Abstract

A method is described to produce global phase diagrams for single-component molecular crystals with separable internal and external modes. The phase diagrams present the equilibrium crystalline phase as a function of the coefficients of a general intermolecular potential based on rotational symmetry-adapted basis functions. It is assumed that phase transitions are driven by orientational ordering of molecules with a fixed time-averaged shape. The mean-field approximation is utilized and the process begins in a high-temperature disordered reference state, then spontaneous symmetry-breaking phase transitions and phase structure information at lower temperature are sought. The information is mapped onto phase diagrams using the intermolecular expansion coefficients as independent variables. This is illustrated by global phase diagrams for molecules having tetrahedral symmetry (e.g. carbon tetrachloride, adamantane and white phosphorus). Uses of global phase diagrams include crystal structure data mining, guidance for crystal design and enumeration of likely or missing polymorphic structures.