Benchmarking magnetizabilities with recent density functionals

TL;DR

This study benchmarks the accuracy of 51 density functionals for predicting magnetizabilities of small molecules, introduces a new numerical integration method for calculating magnetizabilities, and visualizes magnetizability density.

Contribution

It provides a comprehensive accuracy assessment of recent and established density functionals for magnetizabilities and introduces a novel numerical approach within the GIMIC framework for their calculation and visualization.

Findings

BHandHLYP yields the most accurate magnetizabilities.

Some Berkeley and Florida functionals also perform well.

Minnesota functionals are generally not recommended for magnetic property calculations.

Abstract

We have assessed the accuracy for magnetic properties of a set of 51 density functional approximations, including both recently published as well as already established functionals. The accuracy assessment considers a series of 27 small molecules and is based on comparing the predicted magnetizabilities to literature reference values calculated using coupled cluster theory with full singles and doubles and perturbative triples [CCSD(T)] employing large basis sets. The most accurate magnetizabilities, defined as the smallest mean absolute error, were obtained with the BHandHLYP functional. Three of the six studied Berkeley functionals and the three range-separated Florida functionals also yield accurate magnetizabilities. Also some older functionals like CAM-B3LYP, KT1, BHLYP (BHandH), B3LYP and PBE0 perform rather well. In contrast, unsatisfactory performance was generally obtained with Minnesota functionals, which are therefore not recommended for calculations of magnetically induced current density susceptibilities, and related magnetic properties such as magnetizabilities and nuclear magnetic shieldings. We also demonstrate that magnetizabilities can be calculated by numerical integration of the magnetizability density; we have implemented this approach as a new feature in the gauge-including magnetically induced current method (GIMIC). Magnetizabilities can be calculated from magnetically induced current density susceptibilities within this approach even when analytical approaches for magnetizabilities as the second derivative of the energy have not been implemented. The magnetizability density can also be visualized, providing additional information that is not otherwise easily accessible on the spatial origin of the magnetizabilities.