Accurate and Efficient Polymorph Energy Ranking with XDM-corrected hybrid DFT

20 October 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Accurate and efficient computation of relative energies of molecular-crystal polymorphs is of central importance for solid-state pharmaceuticals and in the field of crystal engineering. In recent years, dispersion corrected density-functional theory (DFT) has emerged as the pre-eminent energy-ranking method for crystal structure prediction (CSP). However, planewave implementations of these methods are hindered by poor scaling for large unit cells and are limited to semi-local functionals that suffer from delocalisation error. In this work, we demonstrate that a recent implementation of the exchange-hole dipole moment (XDM) dispersion correction in the Fritz Haber Institute ab initio molecular simulation (FHI-aims) package provides excellent performance for the energy ranking step of CSP. Thanks to its use of highly optimized numerical atom-centred orbitals, FHI-aims provides effectively linear scaling with system size and allows efficient use of hybrid density functionals with minimal basis-set incompleteness errors. We assess the performance of this methodology for the 26 compounds that formed the first 6 CSP blind tests. The hybrid results show significant improvements for 4/26 compounds, where delocalisation error affects the quality of predicted crystal-energy landscapes


Density Functional Theory
Crystal Structure Prediction
Delocalisation Error
crystal energy landscapes


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