Range-separated meta-GGA functional designed for noncovalent interactions

TL;DR

A new range-separated meta-GGA functional tailored for noncovalent interactions improves accuracy by addressing density region errors, dispersion double counting, and correlation-exchange error compensation, showing excellent performance on diverse benchmarks.

Contribution

This work introduces a novel exchange-correlation functional combining range-separated PBEsol exchange with a semilocal correlation functional and dispersion corrections, specifically designed for noncovalent interactions.

Findings

Outstanding performance on water clusters and ionic hydrogen bonds.

Accurate thermochemistry of n-alkane fragmentation.

Effective handling of diverse noncovalent interactions.

Abstract

The accuracy of applying density functional theory to noncovalent interactions is hindered by errors arising from low-density regions of interaction-induced change in the density gradient, error compensation between correlation and exchange functionals, and dispersion double counting. A new exchange-correlation functional designed for noncovalent interactions is proposed to address these problems. The functional consists of the range-separated PBEsol exchange considered in two variants, pure and hybrid, and the semilocal correlation functional of Modrzejewski et al. [J. Chem. Phys. 137, 204121 (2012)] designed with the constraint satisfaction technique to smoothly connect with a dispersion term. Two variants of dispersion correction are appended to the correlation functional: the atom-atom pairwise additive DFT-D3 model and the density-dependent many-body dispersion with self-consistent screening (MBD-rsSCS). From these building blocks a set of four functionals is created to systematically examine the role of pure versus hybrid exchange and the underlying models for dispersion. The new functional is extensively tested on benchmark sets with diverse nature and size. The truly outstanding performance is demonstrated for water clusters of varying size, ionic hydrogen bonds, and thermochemistry of isodesmic n-alkane fragmentation reactions. The merits of each component of the new functional are discussed.