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Kohn–Sham energy decomposition for molecules in a magnetic field

Reimann, Sarah; Borgoo, Alex; Austad, Jon; Tellgren, Erik I.; Teale, Andrew M.; Helgaker, Trygve; Stopkowicz, Stella

Authors

Sarah Reimann

Alex Borgoo

Jon Austad

Erik I. Tellgren

Trygve Helgaker

Stella Stopkowicz



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.

Citation

Reimann, S., Borgoo, A., Austad, J., Tellgren, E. I., Teale, A. M., Helgaker, T., & Stopkowicz, S. (2019). Kohn–Sham energy decomposition for molecules in a magnetic field. Molecular Physics, 117(1), 97-109. doi:10.1080/00268976.2018.1495849

Journal Article Type Article
Acceptance Date Jun 19, 2018
Online Publication Date Jul 18, 2018
Publication Date 2019
Deposit Date Jul 4, 2018
Publicly Available Date Jul 19, 2019
Journal Molecular Physics
Print ISSN 0026-8976
Electronic ISSN 1362-3028
Publisher Taylor & Francis
Peer Reviewed Peer Reviewed
Volume 117
Issue 1
Pages 97-109
DOI https://doi.org/10.1080/00268976.2018.1495849
Keywords electron correlation, density-functional theory, current density-functional theory, magnetic-field density-functional theory, coupled-cluster theory, molecular magnetic properties, strong magnetic fields
Public URL http://eprints.nottingham.ac.uk/id/eprint/52748
Publisher URL https://www.tandfonline.com/doi/full/10.1080/00268976.2018.1495849
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingh.../end_user_agreement.pdf
Additional Information This is an Accepted Manuscript of an article published by Taylor & Francis in Molecular Physics on 18 July 2018, available online: http://www.tandfonline....0/00268976.2018.1495849

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://eprints.nottingham.ac.uk/end_user_agreement.pdf





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