Benchmarking Density Functional Approximations for Diamagnetic and Paramagnetic Molecules in Nonuniform Magnetic Fields

Abstract

In this article, 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 article, we propose a more fine-grained classification of molecular systems on the basis of their response to generally nonuniform magnetic fields. The relation of orientation to different qualitative responses is also considered.