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.

Department of Chemistry University of California Riverside California 92521 USA Email

Department of Physical Chemistry University of Chemistry and Technology Prague Technická 5 CZ 16628 Prague 6 Czech Republic Email

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The seventh blind test of crystal structure prediction: structure ranking methods

First-Principles Models of Polymorphism of Pharmaceuticals: Maximizing the Accuracy-to-Cost Ratio