Multimer Embedding Approach for Molecular Crystals up to Harmonic Vibrational Properties

Abstract

Accurate calculations of molecular crystals are crucial for drug design and crystal engineering. However, periodic high-level density functional calculations using hybrid functionals are often prohibitively expensive for the relevant systems. These expensive periodic calculations can be circumvented by the usage of embedding methods in which, for instance, the periodic calculation is only performed at a lower-cost level and then monomer energies and dimer interactions are replaced by those of the higher-level method. Herein, we extend such a multimer embedding approach to enable energy corrections for trimer interactions and the calculation of harmonic vibrational properties up to the dimer level. We evaluate this approach for the X23 benchmark set of molecular crystals by approximating a periodic hybrid density functional (PBE0+MBD) by embedding multimers into less expensive calculations using a generalized-gradient approximation functional (PBE+MBD). We show that trimer interactions are crucial for accurately approximating lattice energies within 1 kJ/mol and might also be needed for further improvement of lattice constants and hence cell volumes. Finally, the vibrational properties are already very well captured at the monomer and dimer level, making it possible to approximate vibrational free energies at room temperature within 1 kJ/mol.

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“…Hoja et al developed and evaluated an approach to accelerate the prediction of energies, forces, etc. of higher level electronic structure methods for molecular crystals via a multimer embedding approach . Weng et al demonstrated how to efficiently and robustly obtain regionally localized orbitals for a subsystem using the generalized Pipek-Mezey scheme, which can be applied to large nanoscale systems without incurring significant computational cost overhead .…”