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Open AccessArticle

Intermolecular Interactions in Molecular Organic Crystals upon Relaxation of Lattice Parameters

Max Planck Institute for Dynamics of Complex Technical Systems, Molecular Simulations and Design Group, Sandtorstrasse 1, 39106 Magdeburg, Germany
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Crystals 2019, 9(12), 665; https://doi.org/10.3390/cryst9120665
Received: 21 November 2019 / Revised: 5 December 2019 / Accepted: 7 December 2019 / Published: 10 December 2019
(This article belongs to the Section Crystal Engineering)
Crystal structure prediction is based on the assumption that the most thermodynamically stable structure will crystallize first. The existence of other structures such as polymorphs or from counterenantiomers requires an accurate calculation of the electronic energy. Using atom-centered Gaussian basis functions in periodic Density Functional Theory (DFT) calculations in Turbomole, the performance of two dispersion-corrected functionals, PBE-D3 and B97-D, is assessed for molecular organic crystals of the X23 benchmark set. B97-D shows a MAE (mean absolute error) of 4 kJ/mol, compared to 9 kJ/mol for PBE-D3. A strategy for the convergence of lattice energies towards the basis set limit is outlined. A simultaneous minimization of molecular structures and lattice parameters shows that both methods are able to reproduce experimental unit cell parameters to within 4–5%. Calculated lattice energies, however, deviate slightly more from the experiment, i.e., by 0.4 kJ/mol after unit cell optimization for PBE-D3 and 0.5 kJ/mol for B97-D. The accuracy of the calculated lattice energies compared to the experimental values demonstrates the ability of current DFT methods to assist in the quest for possible polymorphs and enantioselective crystallization processes. View Full-Text
Keywords: lattice energy; crystal packing; noncovalent interactions; unit cell optimization; van der Waals; periodic DFT lattice energy; crystal packing; noncovalent interactions; unit cell optimization; van der Waals; periodic DFT
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Stein, M.; Heimsaat, M. Intermolecular Interactions in Molecular Organic Crystals upon Relaxation of Lattice Parameters. Crystals 2019, 9, 665.

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