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 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

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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.

Item Type: Article
Additional Information: This is the peer reviewed version of the following article: E. I. Tellgren, A. M. Teale, J. W. Furness, K. K. Lange, U. Ekström, and T. Helgaker, The Journal of Chemical Physics 140, 034101 (2014), American Institute of Physics
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number:
Depositing User: Teale, Andrew
Date Deposited: 17 Dec 2015 09:45
Last Modified: 04 May 2020 16:41

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