TY - JOUR

T1 - Computational Investigation of the Stability of Di-p-Tolyl Disulfide “Hidden” and “Conventional” Polymorphs at High Pressures

AU - Smirnova, Valeriya Yu

AU - Iurchenkova, Anna A.

AU - Rychkov, Denis A.

N1 - Funding Information: This research was funded by Ministry of Higher Education and Science, grant number FWUS-2021-0005 (FF and periodic DFT calculations, data processing and analysis) and the Russian Science Foundation, grant number 18-73-00154 (system choice, database search, preliminary calculations). Publisher Copyright: © 2022 by the authors.

PY - 2022/8

Y1 - 2022/8

N2 - The investigation of molecular crystals at high pressure is a sought-after trend in crystallography, pharmaceutics, solid state chemistry, and materials sciences. The di-p-tolyl disulfide (CH3−C6H4−S−)2 system is a bright example of high-pressure polymorphism. It contains “conventional” solid–solid transition and a “hidden” form which may be obtained only from solution at elevated pressure. In this work, we apply force field and periodic DFT computational techniques to evaluate the thermodynamic stability of three di-p-tolyl disulfide polymorphs as a function of pressure. Theoretical pressures and driving forces for polymorphic transitions are defined, showing that the compressibility of the γ phase is the key point for higher stability at elevated pressures. Transition state energies are also estimated for α → β and α → γ transitions from thermodynamic characteristics of crystal structures, not exceeding 5 kJ/mol. The β → γ transition does not occur experimentally in the 0.0–2.8 GPa pressure range because transition state energy is greater than 18 kJ/mol. Relations between free Gibbs energy (in assumption of enthalpy) of phases α, β, and γ, as a function of pressure, are suggested to supplement and refine experimental data. A brief discussion of the computational techniques used for high-pressure phase transitions is provided.

AB - The investigation of molecular crystals at high pressure is a sought-after trend in crystallography, pharmaceutics, solid state chemistry, and materials sciences. The di-p-tolyl disulfide (CH3−C6H4−S−)2 system is a bright example of high-pressure polymorphism. It contains “conventional” solid–solid transition and a “hidden” form which may be obtained only from solution at elevated pressure. In this work, we apply force field and periodic DFT computational techniques to evaluate the thermodynamic stability of three di-p-tolyl disulfide polymorphs as a function of pressure. Theoretical pressures and driving forces for polymorphic transitions are defined, showing that the compressibility of the γ phase is the key point for higher stability at elevated pressures. Transition state energies are also estimated for α → β and α → γ transitions from thermodynamic characteristics of crystal structures, not exceeding 5 kJ/mol. The β → γ transition does not occur experimentally in the 0.0–2.8 GPa pressure range because transition state energy is greater than 18 kJ/mol. Relations between free Gibbs energy (in assumption of enthalpy) of phases α, β, and γ, as a function of pressure, are suggested to supplement and refine experimental data. A brief discussion of the computational techniques used for high-pressure phase transitions is provided.

KW - di-p-tolyl disulfide

KW - hidden polymorph

KW - high-pressure DFT

KW - high-pressure polymorph

KW - molecular crystals

KW - relative stability

UR - http://www.scopus.com/inward/record.url?scp=85137408463&partnerID=8YFLogxK

U2 - 10.3390/cryst12081157

DO - 10.3390/cryst12081157

M3 - Article

AN - SCOPUS:85137408463

VL - 12

JO - Crystals

JF - Crystals

SN - 2073-4352

IS - 8

M1 - 1157

ER -