@article { , title = {Kohn–Sham energy decomposition for molecules in a magnetic field}, abstract = {We study the total molecular electronic energy and its Kohn–Sham components within the framework of magnetic-field density-functional theory (BDFT), an alternative to current-dependent density-functional theory (CDFT) for molecules in the presence of magnetic fields. For a selection of closed-shell dia- and paramagnetic molecules, we investigate the dependence of the total electronic energy and its Kohn–Sham components on the magnetic field. Results obtained from commonly used density-functional approximations are compared with those obtained from Lieb optimizations based on magnetic-field dependent relaxed coupled-cluster singles-and-doubles (CCSD) and second-order Møller–Plesset (MP2) densities. We show that popular approximate exchange–correlation functionals at the generalized-gradient-approximation (GGA), meta-GGA, and hybrid levels of theory provide a good qualitative description of the electronic energy and its Kohn–Sham components in a magnetic field—in particular, for the diamagnetic molecules. The performance of Hartree–Fock theory, MP2 theory, CCSD theory and BDFT with different exchange–correlation functionals is compared with coupled-cluster singles-doubles-perturbative-triples (CCSD(T)) theory for the perpendicular component of the magnetizability. Generalizations of the TPSS meta-GGA functional to systems in a magnetic field work well—the cTPSS functional, in particular, with a current-corrected kinetic-energy density, performs excellently, providing an accurate and balanced treatment of dia- and paramagnetic systems and outperforming MP2 theory.}, doi = {10.1080/00268976.2018.1495849}, eissn = {1362-3028}, issn = {0026-8976}, issue = {1}, journal = {Molecular Physics}, note = {12 months embargo. Ol 04.07.2018. Updated OL 07.08.2018}, pages = {97-109}, publicationstatus = {Published}, publisher = {Taylor and Francis}, url = {https://nottingham-repository.worktribe.com/output/939322}, volume = {117}, keyword = {electron correlation, density-functional theory, current density-functional theory, magnetic-field density-functional theory, coupled-cluster theory, molecular magnetic properties, strong magnetic fields}, year = {2024}, author = {Reimann, Sarah and Borgoo, Alex and Austad, Jon and Tellgren, Erik I. and Teale, Andrew M. and Helgaker, Trygve and Stopkowicz, Stella} }