Fundamental Role of Fock Exchange in Relativistic Density Functional Theory
| Autor: | Jean-Pierre Flament, Alessandro Erba, Jacques K. Desmarais |
|---|---|
| Přispěvatelé: | Dipartimento di Chimica IFM and NIS, Università degli studi di Torino (UNITO), Department of Geological Sciences, University of Saskatchewan [Saskatoon] (U of S), Department of Physics and Engineering Physics [Saskatoon], Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Università degli studi di Torino = University of Turin (UNITO) |
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Physics
Density matrix Spinor Operator (physics) Diagonal 02 engineering and technology 021001 nanoscience & nanotechnology Coupling (probability) 01 natural sciences Fock space [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Theoretical physics Magnetization 0103 physical sciences General Materials Science Density functional theory [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] Physical and Theoretical Chemistry 010306 general physics 0210 nano-technology ComputingMilieux_MISCELLANEOUS |
| Zdroj: | Journal of Physical Chemistry Letters Journal of Physical Chemistry Letters, American Chemical Society, 2019, 10, pp.3580-3585. ⟨10.1021/acs.jpclett.9b01401⟩ Journal of Physical Chemistry Letters, 2019, 10, pp.3580-3585. ⟨10.1021/acs.jpclett.9b01401⟩ |
| ISSN: | 1948-7185 |
| DOI: | 10.1021/acs.jpclett.9b01401⟩ |
| Popis: | We perform a formal analysis of relativistic density functional theory for the treatment of spin-orbit coupling (SOC), noncollinear magnetization (NCM), and orbital current density (OCD). We identify specific components of the spinors (namely, those mapped onto imaginary diagonal spin-blocks of the density matrix) that arise from the SOC operator and define the OCD. We show that these pieces of the spinors only enter in the bielectronic part of the potential through the exact Fock exchange (FE) operator. The lack of FE therefore leads to a correspondingly incorrect physical description of SOC, NCM, and OCD. This analysis is complemented with an illustrative example, where we show that, while in the absence of FE, the theory fails even at reproducing the expected right-hand relationship between the NCM and OCD, its inclusion provides results that match those from a reference SOC configuration-interaction calculation. |
| Databáze: | OpenAIRE |
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