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High‐pressure Nucleation of Low‐Density Polymorphs **
Author(s) -
Sobczak Szymon,
Ratajczyk Paulina,
Katrusiak Andrzej
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202005121
Subject(s) - nucleation , thermodynamics , crystallization , kinetic energy , high pressure , polymorphism (computer science) , materials science , entropy (arrow of time) , crystallography , ambient pressure , chemistry , biochemistry , physics , quantum mechanics , genotype , gene
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.