TY - JOUR

T1 - Simple Fully Nonlocal Density Functionals for Electronic Repulsion Energy

AU - Vuckovic, Stefan

AU - Gori-Giorgi, Paola

PY - 2017/7/6

Y1 - 2017/7/6

N2 - From a simplified version of the mathematical structure of the strong coupling limit of the exact exchange-correlation functional, we construct an approximation for the electronic repulsion energy at physical coupling strength, which is fully nonlocal. This functional is self-interaction free and yields energy densities within the definition of the electrostatic potential of the exchange-correlation hole that are locally accurate and have the correct asymptotic behavior. The model is able to capture strong correlation effects that arise from chemical bond dissociation, without relying on error cancellation. These features, which are usually missed by standard density functional theory (DFT) functionals, are captured by the highly nonlocal structure, which goes beyond the "Jacob's ladder" framework for functional construction, by using integrals of the density as the key ingredient. Possible routes for obtaining the full exchange-correlation functional by recovering the missing kinetic component of the correlation energy are also implemented and discussed.

AB - From a simplified version of the mathematical structure of the strong coupling limit of the exact exchange-correlation functional, we construct an approximation for the electronic repulsion energy at physical coupling strength, which is fully nonlocal. This functional is self-interaction free and yields energy densities within the definition of the electrostatic potential of the exchange-correlation hole that are locally accurate and have the correct asymptotic behavior. The model is able to capture strong correlation effects that arise from chemical bond dissociation, without relying on error cancellation. These features, which are usually missed by standard density functional theory (DFT) functionals, are captured by the highly nonlocal structure, which goes beyond the "Jacob's ladder" framework for functional construction, by using integrals of the density as the key ingredient. Possible routes for obtaining the full exchange-correlation functional by recovering the missing kinetic component of the correlation energy are also implemented and discussed.

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U2 - 10.1021/acs.jpclett.7b01113

DO - 10.1021/acs.jpclett.7b01113

M3 - Article

AN - SCOPUS:85022056524

VL - 8

SP - 2799

EP - 2805

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

SN - 1948-7185

IS - 13

ER -