Improving intermolecular interactions in DFTB3 using extended polarization from chemical-potential equalization

TL;DR

This paper enhances the DFTB3 semi-empirical method by incorporating an auxiliary response density via chemical-potential equalization and empirical dispersion correction, significantly improving accuracy for intermolecular interactions involving charged species.

Contribution

It introduces a CPE extension to DFTB3-D3, fitted to high-level reference data, improving interaction energy predictions especially for charged and polar molecules.

Findings

RMSD for charged interactions reduced from 6.07 to 1.49 kcal/mol

Salt bridge interaction RMSD improved from 5.60 to 1.73 kcal/mol

Polarizabilities of neutral molecules are notably improved

Abstract

Semi-empirical quantum mechanical methods traditionally expand the electron density in a minimal, valence-only electron basis set. The minimal-basis approximation causes molecular polarization to be underestimated, and hence intermolecular interaction energies are also underestimated, especially for intermolecular interactions involving charged species. In this work, the third-order self-consistent charge density functional tight-binding method (DFTB3) is augmented with an auxiliary response density using the chemical-potential equalization (CPE) method and an empirical dispersion correction (D3). The parameters in the CPE and D3 models are fitted to high-level CCSD(T) reference interaction energies for a broad range of chemical species, as well as dipole moments calculated at the DFT level; the impact of including polarizabilities of molecules in the parameterization is also considered. Parameters for the elements H, C, N, O and S are presented. The RMSD interaction energy is improved from 6.07 kcal/mol to 1.49 kcal/mol for interactions with one charged specie, whereas the RMSD is improved from 5.60 kcal/mol to 1.73 for a set of 9 salt bridges, compared to uncorrected DFTB3. For large water clusters and complexes that are dominated by dispersion interactions, the already satisfactory performance of the DFTB3-D3 model is retained; polarizabilities of neutral molecules are also notably improved. Overall, the CPE extension of DFTB3-D3 provides a more balanced description of different types of non-covalent interactions than NDDO type of semi-empirical methods (e.g., PM6-D3H4) and PBE-D3 with modest basis sets.