High-pressure Nucleation of Low-Density Polymorphs*

Abstract

New polymorphs β and γ of bis-3-nitrophenyl disulphide, crystallized above 0.3 GPa, are less dense than the ambient-pressure polymorph α. This counterintuitive density relation results from the high-entropy nucleation and subsequent kinetic crystallization. The work performed by pressure compensates the high entropy and temperature product, substantiated in varied conformers and increased chemical potential. Pressure-increased viscosity promotes the kinetic polymorphs, in accordance with empirical Ostwald's rule of stages. It contrasts to mechanochemical techniques, favouring high-density polymorphs.