Kohn–Sham energy decomposition for molecules in a magnetic field

Reimann, Sarah, Borgoo, Alex, Austad, Jon, Tellgren, Erik I., Teale, Andrew M., Helgaker, Trygve and Stopkowicz, Stella (2019) Kohn–Sham energy decomposition for molecules in a magnetic field. Molecular Physics, 117 (1). pp. 97-109. ISSN 1362-3028

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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.

Item Type: Article
RIS ID: https://nottingham-repository.worktribe.com/output/939322
Keywords: electron correlation, density-functional theory, current density-functional theory, magnetic-field density-functional theory, coupled-cluster theory, molecular magnetic properties, strong magnetic fields
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number: https://doi.org/10.1080/00268976.2018.1495849
Depositing User: Teale, Andrew
Date Deposited: 04 Jul 2018 08:07
Last Modified: 04 May 2020 19:41
URI: https://eprints.nottingham.ac.uk/id/eprint/52748

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