Benchmarking density functional approximations for diamagnetic and paramagnetic molecules in nonuniform magnetic fields

TL;DR

This study benchmarks various density functional approximations against wavefunction methods for their accuracy in predicting magnetic response properties of small molecules in non-uniform magnetic fields, introducing a refined classification based on response behavior.

Contribution

It introduces a detailed classification of molecules based on their response to non-uniform magnetic fields and benchmarks density functional methods against high-level wavefunction calculations for these properties.

Findings

Density functional approximations show varying accuracy in predicting magnetic susceptibilities.

A new classification scheme for molecules based on non-uniform magnetic field response.

Benchmark results highlight strengths and limitations of current DFT methods.

Abstract

In this paper, correlated studies on a test set of 36 small molecules are carried out with both wavefunction (HF, MP2, CCSD) and density functional (LDA, KT3, cTPSS, cM06-L) methods. The effect of correlation on exotic response properties such as molecular electronic anapole susceptibilities is studied and the performance of the various density functional approximations are benchmarked against CCSD and/or MP2. Atoms and molecules are traditionally classified into `diamagnetic' and `paramagnetic' based on their isotropic response to uniform magnetic fields. However, in this paper we propose a more fine-grained classification of molecular systems on the basis of their response to generally non-uniform magnetic fields. The relation of orientation to different qualitative responses is also considered.