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Magnetic-Field Density-Functional Theory (BDFT): Lessons from the Adiabatic Connection

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Department of Chemistry, Hylleraas Centre for Quantum Molecular Sciences, University of Oslo, P.O. Box 1033, Blindern, Oslo N-0315, Norway
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, U.K.
Cite this: J. Chem. Theory Comput. 2017, 13, 9, 4089–4100
Publication Date (Web):August 2, 2017
https://doi.org/10.1021/acs.jctc.7b00295
Copyright © 2017 American Chemical Society
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Abstract

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We study the effects of magnetic fields in the context of magnetic field density-functional theory (BDFT), where the energy is a functional of the electron density ρ and the magnetic field B. We show that this approach is a worthwhile alternative to current-density functional theory (CDFT) and may provide a viable route to the study of many magnetic phenomena using density-functional theory (DFT). The relationship between BDFT and CDFT is developed and clarified within the framework of the four-way correspondence of saddle functions and their convex and concave parents in convex analysis. By decomposing the energy into its Kohn–Sham components, we demonstrate that the magnetizability is mainly determined by those energy components that are related to the density. For existing density functional approximations, this implies that, for the magnetizability, improvements of the density will be more beneficial than introducing a magnetic-field dependence in the correlation functional. However, once a good charge density is achieved, we show that high accuracy is likely only obtainable by including magnetic-field dependence. We demonstrate that adiabatic-connection (AC) curves at different field strengths resemble one another closely provided each curve is calculated at the equilibrium geometry of that field strength. In contrast, if all AC curves are calculated at the equilibrium geometry of the field-free system, then the curves change strongly with increasing field strength due to the increasing importance of static correlation. This holds also for density functional approximations, for which we demonstrate that the main error encountered in the presence of a field is already present at zero field strength, indicating that density-functional approximations may be applied to systems in strong fields, without the need to treat additional static correlation.

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