XDM-Corrected Hybrid DFT with Numerical Atomic Orbitals Predicts Molecular Crystal Lattice Energies with Unprecedented Accuracy

01 November 2022, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


Molecular crystals are important for many applications, including energetic materials, organic semi-conductors, and the development and commercialization of pharmaceuticals. The exchange-hole dipole moment (XDM) dispersion model has shown good performance in the calculation of relative and absolute lattice energies of molecular crystals, although it has traditionally been applied in combination with plane-wave/pseudopotential approaches. This has limited XDM to use with semilocal functional approximations, which suffer from delocalization error and poor quality conformational energies, and to systems with a few hundreds of atoms at most due to unfavorable scaling. In this work, we combine XDM with numerical atomic orbitals, which enable the efficient use of XDM-corrected hybrid functionals for molecular crystals. This improves the treatment of delocalization error and conformational energies, and makes the calculation scale linearly with system size. We test the new XDM-corrected functionals for their ability to predict the lattice energies of molecular crystals for the X23 set and 13 ice phases, the latter being a particularly stringent test. A composite approach using a XDM-corrected, 25% hybrid functional based on B86bPBE achieves a mean absolute error of 0.48 kcal/mol per molecule for the X23 set and 0.19 kcal/mol for the total lattice energies of the ice phases, compared to recent diffusion Monte-Carlo data. These results make the new XDM-corrected hybrids not only far more computationally efficient than previous XDM implementations, but also the most accurate density-functional methods for molecular crystal lattice energies to date.


molecular crystals
lattice energies


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