Kohn–Sham energy decomposition for molecules in a magnetic field
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...
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Taylor & Francis
2019
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| Online Access: | https://eprints.nottingham.ac.uk/52748/ |
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| author | Reimann, Sarah Borgoo, Alex Austad, Jon Tellgren, Erik I. Teale, Andrew M. Helgaker, Trygve Stopkowicz, Stella |
| author_facet | Reimann, Sarah Borgoo, Alex Austad, Jon Tellgren, Erik I. Teale, Andrew M. Helgaker, Trygve Stopkowicz, Stella |
| author_sort | Reimann, Sarah |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
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| format | Article |
| id | nottingham-52748 |
| institution | University of Nottingham Malaysia Campus |
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| last_indexed | 2025-11-14T20:25:31Z |
| publishDate | 2019 |
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| spelling | nottingham-527482020-05-04T19:41:22Z https://eprints.nottingham.ac.uk/52748/ 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 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. Taylor & Francis 2019 Article PeerReviewed 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 electron correlation density-functional theory current density-functional theory magnetic-field density-functional theory coupled-cluster theory molecular magnetic properties strong magnetic fields https://www.tandfonline.com/doi/full/10.1080/00268976.2018.1495849 doi:10.1080/00268976.2018.1495849 doi:10.1080/00268976.2018.1495849 |
| spellingShingle | electron correlation density-functional theory current density-functional theory magnetic-field density-functional theory coupled-cluster theory molecular magnetic properties strong magnetic fields Reimann, Sarah Borgoo, Alex Austad, Jon Tellgren, Erik I. Teale, Andrew M. Helgaker, Trygve Stopkowicz, Stella Kohn–Sham energy decomposition for molecules in a magnetic field |
| title | Kohn–Sham energy decomposition for molecules in a magnetic field |
| title_full | Kohn–Sham energy decomposition for molecules in a magnetic field |
| title_fullStr | Kohn–Sham energy decomposition for molecules in a magnetic field |
| title_full_unstemmed | Kohn–Sham energy decomposition for molecules in a magnetic field |
| title_short | Kohn–Sham energy decomposition for molecules in a magnetic field |
| title_sort | kohn–sham energy decomposition for molecules in a magnetic field |
| topic | electron correlation density-functional theory current density-functional theory magnetic-field density-functional theory coupled-cluster theory molecular magnetic properties strong magnetic fields |
| url | https://eprints.nottingham.ac.uk/52748/ https://eprints.nottingham.ac.uk/52748/ https://eprints.nottingham.ac.uk/52748/ |