Accurate lattice energies of organic molecular crystals from periodic turbomole calculations

• Published in: Journal of computational chemistry 2018-07, Vol.39 (19), p.1335-1343
• Main Authors: Buchholz, Hannes Konrad, Stein, Matthias
• Format: Article
• Language: English
• Subjects: Basis functions; Benzoic acid; chiral; Crystal lattices; Crystals; Lattice energy; Mathematical analysis; Molecular chains; molecular crystals; Naphthalene; Organic chemistry; Organic crystals; periodic DFT; Pharmaceutical industry; Separation processes
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.25205

Accurate lattice energies of organic crystals are important i.e. for the pharmaceutical industry. Periodic DFT calculations with atom‐centered Gaussian basis functions with the Turbomole program are used to calculate lattice energies for several non‐covalently bound organic molecular crystals. The accuracy and convergence of results with basis set size and k‐space sampling from periodic calculations is evaluated for the two reference molecules benzoic acid and naphthalene. For the X23 benchmark set of small molecular crystals accurate lattice energies are obtained using the PBE‐D3 functional. In particular for hydrogen‐bonded systems, a sufficiently large basis set is required. The calculated lattice energy differences between enantiopure and racemic crystal forms for a prototype set of chiral molecules are in good agreement with experimental results and allow the rationalization and computer‐aided design of chiral separation processes. © 2018 Wiley Periodicals, Inc. The accuracy of atom‐centered Gaussian basis functions for the X23 benchmark set of organic molecular crystals was demonstrated. Periodic Turbomole calculations allow the precise calculation of small lattice energy differences between enantiopure and racemic crystals of chiral compounds.