Current Density Functional Theory Using Meta-Generalized Gradient Exchange-Correlation Functionals

Furness, James W.; Verbeke, Joachim; Tellgren, Erik I.; Stopkowicz, Stella; Ekström, Ulf; Helgaker, Trygve; Teale, Andrew M.

doi:10.1021/acs.jctc.5b00535

Cited by 81 publications

(120 citation statements)

References 60 publications

(187 reference statements)

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“…[25,27,[30][31][32][33][34] for further discussion). This unphysical dependence can be removed by introducing terms dependent on the paramagnetic current density, such as those that arise in the discussion of the spherical average of the exchange hole by Dobson [30].…”

Section: Extension Of Elf To Magnetic Fieldsmentioning

confidence: 99%

“…Recently, we have studied exchange-correlation functionals in current DFT (CDFT) for calculations of molecules in the presence of strong uniform magnetic fields [22][23][24][25]. In particular, in Ref.…”

Section: Introductionmentioning

confidence: 99%

“…In particular, in Ref. [25], we showed that the current-dependent generalisation of the Tao-Perdew-Staroverov-Scuseria (TPSS) meta-generalisedgradient-approximation (meta-GGA) functional [26], denoted cTPSS (see also Ref. [27] for the use of cTPSS in response theory) provides a reasonable description of molecules in strong magnetic fields.…”

Section: Introductionmentioning

confidence: 99%

“…The nature of this bonding interaction was accurately captured and analysed in terms of molecular-orbital energies and electron-density differences at the CDFT level in Ref. [25] using the cTPSS functional.…”

Section: Introductionmentioning

confidence: 99%

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Electron localisation function in current-density-functional theory

et al. 2016

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We present a generalisation of the electron localisation function (ELF) to current-densityfunctional theory as a descriptor for the properties of molecules in the presence of magnetic fields. The resulting current ELF (cELF) is examined for a range of small molecular systems in field strengths up to B 0 = 235 kT (one atomic unit). The cELF clearly depicts the compression of the molecular electronic structure in the directions perpendicular to the applied field and exhibits a structure similar to that of the physical current densities. A topological analysis is performed to examine the changes in chemical bonding upon application of a magnetic field.

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Section: Extension Of Elf To Magnetic Fieldsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electron localisation function in current-density-functional theory

et al. 2016

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“…The development of such functionals is an active field of research. [7][8][9] In this paper, we analyse for the first time the field dependence of the Kohn-Sham energy components, using the adiabatic connection (AC).…”

Section: Introductionmentioning

confidence: 99%

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

Reimann

Borgoo

Tellgren

et al. 2017

J. Chem. Theory Comput.

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We study the e↵ects of magnetic fields in the context of magnetic field densityfunctional theory (BDFT), where the energy is a functional of the electron density ⇢ 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 fourway 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 1 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 di↵erent 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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External fields in conceptual density functional theory

Geerlings

Proft

2022

J Comput Chem

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The necessity of the recent incorporation of new external variables in the context of conceptual DFT (CDFT) is discussed based on the ever‐increasing portfolio of experimental reaction conditions in the endeavor of experimentalists to synthesize new molecules with unprecedented properties. Electric and magnetic fields (ε and B), mechanical forces (F), and confinement are proposed as valuable new variables, extending conventional CDFT and its associated response functions. A finite field approach is used to calculate the evolution of both global and local descriptors in a selected series of atomic and molecular applications, and from it derive new response function involving, with one exception, the first derivative to the field considered. The electric field results, displaying, for example, a case of a field‐induced enantioselectivity in the Fukui function, may be instrumental in the recent upsurge of chemistry in oriented external electric fields. The study of atomic electronegativity and hardness in magnetic fields displays a piecewise behavior, associated to configurational jumps upon increasing field strength and reveals an overall compression of their ranges for stronger fields, which may be guiding upon investigating chemistry in extremely high fields like in white dwarfs. The evolution of the electronegativity and hardness of diatomics under mechanical force can elegantly be traced back to differences in their equilibrium distance in the neutral, cationic, and anionic state. The well‐known reduction of the polarizability under confinement can be seen as a fore‐runner of the increasing hardness of atoms under pressure, presently under investigation. Periodicity showing up in a spontaneous way in the variety of properties is a leitmotiv in this study, as well as the interconnections/analogies between the different response functions.

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Current Density Functional Theory Using Meta-Generalized Gradient Exchange-Correlation Functionals

Cited by 81 publications

References 60 publications

Electron localisation function in current-density-functional theory

Electron localisation function in current-density-functional theory

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

External fields in conceptual density functional theory

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