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Study of Self-Interaction Errors in Density Functional Calculations of Magnetic Exchange Coupling Constants Using Three Self-Interaction Correction Methods

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [2];  [3];  [3];  [2];  [2]
  1. Univ. of Texas at El Paso, TX (United States); University of Texas at El Paso
  2. Univ. of Texas at El Paso, TX (United States)
  3. Central Michigan Univ., Mount Pleasant, MI (United States)
+ Show Author Affiliations
We examine the role of self-interaction errors (SIE) removal on the evaluation of magnetic exchange coupling constants. In particular we analyze the effect of scaling down the self-interaction-correction (SIC) for three non-empirical density functional approximations (DFAs) namely, the local spin density approximation, the Perdew-Burke-Ernzerhof generalized gradient approximation, and recent SCAN family of meta-GGA functionals. To this end, we employ three one-electron SIC methods: Perdew-Zunger [Perdew, J. P.; Zunger, A. Phys. Rev. B, 1981, 23, 5048] SIC, the orbitalwise scaled SIC method [Vydrov, O. A. et al., J. Chem. Phys. 2006, 124, 094108], and the recent local scaling method [Zope, R. R. et al., J. Chem. Phys. 2019, 151, 214108]. We compute the magnetic exchange coupling constants using the spin projection and non projection approaches for sets of molecules composed of dinuclear and polynuclear H-He models, organic radical molecules, and chlorocuprate, and compare these results against accurate theories and experiment. Our results show that for the systems that mainly consist of single electron regions, PZSIC performs well but for more complex organic systems and the chlorcuprates, an overcorrecting tendency of PZSIC combined with the DFAs utilized in this work is more pronounced, and in such cases LSIC with kinetic energy density ratio performs better than PZSIC. Furthermore, analysis of the results in terms of SIC corrections to the density and to the total energy shows that both density and energy correction are required to obtain an improved prediction of magnetic exchange couplings.
Research Organization:
Central Michigan Univ., Mount Pleasant, MI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0018331
OSTI ID:
1860638
Alternate ID(s):
OSTI ID: 1866254
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 12 Vol. 126; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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