Issue 20, 2018

Ab initio prediction of the polymorph phase diagram for crystalline methanol

Abstract

Organic crystals frequently adopt multiple distinct polymorphs exhibiting different properties. The ability to predict not only what crystal forms might occur, but under what experimental thermodynamic conditions those polymorphs are stable would be immensely valuable to the pharmaceutical industry and others. Starting only from knowledge of the experimental crystal structures, this study successfully predicts the methanol crystal polymorph phase diagram from first-principles quantum chemistry, mapping out the thermodynamic regions of stability for three polymorphs over the range 0–400 K and 0–6 GPa. The agreement between the predicted and experimental phase diagrams corresponds to predicting the relative polymorph free energies to within ∼0.5 kJ mol−1 accuracy, which is achieved by employing fragment-based second-order Møller–Plesset perturbation theory and coupled cluster theory plus a quasi-harmonic treatment of the phonons.

Graphical abstract: Ab initio prediction of the polymorph phase diagram for crystalline methanol

Supplementary files

Article information

Article type
Edge Article
Submitted
15 Marts 2018
Accepted
13 Apr. 2018
First published
16 Apr. 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2018,9, 4622-4629

Ab initio prediction of the polymorph phase diagram for crystalline methanol

C. Červinka and G. J. O. Beran, Chem. Sci., 2018, 9, 4622 DOI: 10.1039/C8SC01237G

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