Non-perturbative calculation of molecular magnetic properties within current-density functional theory
We present a novel implementation of Kohn-Sham density-functional theory utilizing London atomic orbitals as basis functions. External magnetic elds are treated non-perturbatively, which enables the study of both magnetic response properties and the effects of strong fields, using either standard de...
| Main Authors: | , , , , , |
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| Format: | Article |
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American Institute of Physics
2014
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| Online Access: | https://eprints.nottingham.ac.uk/31104/ |
| _version_ | 1848794128465264640 |
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| author | Tellgren, Erik I. Teale, Andrew M. Furness, James W. Lange, K.K. Ekström, Ulf Helgaker, Trygve |
| author_facet | Tellgren, Erik I. Teale, Andrew M. Furness, James W. Lange, K.K. Ekström, Ulf Helgaker, Trygve |
| author_sort | Tellgren, Erik I. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | We present a novel implementation of Kohn-Sham density-functional theory utilizing London atomic orbitals as basis functions. External magnetic elds are treated non-perturbatively, which enables the study of both magnetic response properties and the effects of strong fields, using either standard density functionals or current-density functionals - the implementation is the first fully self-consistent implementation of the latter for molecules. Pilot applications are presented for the finite-field calculation of molecular magnetizabilities, hypermagnetizabilities and nuclear magnetic resonance shielding constants, focusing on the impact of current-density functionals on the accuracy of the results. Existing current-density functionals based on the gauge-invariant vorticity are tested and found to be sensitive to numerical details of their implementation. Furthermore, when appropriately regularized, the resulting magnetic properties show no improvement over standard density-functional results. An advantage of the present implementation is the ability to apply density-functional theory to molecules in very strong magnetic fields, where the perturbative approach breaks down. Comparison with high accuracy full-conguration-interaction results shows that the inadequacies of current-density approximations are exacerbated with increasing magnetic field strength. Standard density-functionals remain well behaved but fail to deliver high accuracy. The need for improved current-dependent density-functionals, and how they may be tested using the presented implementation, is discussed in light of our findings. |
| first_indexed | 2025-11-14T19:11:16Z |
| format | Article |
| id | nottingham-31104 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:11:16Z |
| publishDate | 2014 |
| publisher | American Institute of Physics |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-311042020-05-04T16:41:47Z https://eprints.nottingham.ac.uk/31104/ Non-perturbative calculation of molecular magnetic properties within current-density functional theory Tellgren, Erik I. Teale, Andrew M. Furness, James W. Lange, K.K. Ekström, Ulf Helgaker, Trygve We present a novel implementation of Kohn-Sham density-functional theory utilizing London atomic orbitals as basis functions. External magnetic elds are treated non-perturbatively, which enables the study of both magnetic response properties and the effects of strong fields, using either standard density functionals or current-density functionals - the implementation is the first fully self-consistent implementation of the latter for molecules. Pilot applications are presented for the finite-field calculation of molecular magnetizabilities, hypermagnetizabilities and nuclear magnetic resonance shielding constants, focusing on the impact of current-density functionals on the accuracy of the results. Existing current-density functionals based on the gauge-invariant vorticity are tested and found to be sensitive to numerical details of their implementation. Furthermore, when appropriately regularized, the resulting magnetic properties show no improvement over standard density-functional results. An advantage of the present implementation is the ability to apply density-functional theory to molecules in very strong magnetic fields, where the perturbative approach breaks down. Comparison with high accuracy full-conguration-interaction results shows that the inadequacies of current-density approximations are exacerbated with increasing magnetic field strength. Standard density-functionals remain well behaved but fail to deliver high accuracy. The need for improved current-dependent density-functionals, and how they may be tested using the presented implementation, is discussed in light of our findings. American Institute of Physics 2014-01-15 Article PeerReviewed Tellgren, Erik I., Teale, Andrew M., Furness, James W., Lange, K.K., Ekström, Ulf and Helgaker, Trygve (2014) Non-perturbative calculation of molecular magnetic properties within current-density functional theory. Journal of Chemical Physics, 140 (3). 034101. ISSN 1089-7690 http://scitation.aip.org/content/aip/journal/jcp/140/3/10.1063/1.4861427 doi:10.1063/1.4861427 doi:10.1063/1.4861427 |
| spellingShingle | Tellgren, Erik I. Teale, Andrew M. Furness, James W. Lange, K.K. Ekström, Ulf Helgaker, Trygve Non-perturbative calculation of molecular magnetic properties within current-density functional theory |
| title | Non-perturbative calculation of molecular magnetic properties within current-density functional theory |
| title_full | Non-perturbative calculation of molecular magnetic properties within current-density functional theory |
| title_fullStr | Non-perturbative calculation of molecular magnetic properties within current-density functional theory |
| title_full_unstemmed | Non-perturbative calculation of molecular magnetic properties within current-density functional theory |
| title_short | Non-perturbative calculation of molecular magnetic properties within current-density functional theory |
| title_sort | non-perturbative calculation of molecular magnetic properties within current-density functional theory |
| url | https://eprints.nottingham.ac.uk/31104/ https://eprints.nottingham.ac.uk/31104/ https://eprints.nottingham.ac.uk/31104/ |