by Kieron Burke, John P. Perdew and Ernzerhof, Matthias
Abstract:
Abstract The local spin density (LSD) approximation, while of only moderate accuracy, has proven extremely reliable over three decades of use. We argue that any gradient-corrected functional should preserve the correct features of LSD even if the system under study contains no regions of small density gradient. The Perdew-Wang 1991 (PW91) functional respects this condition, while, e.g., the Lee-Yang-Parr (LYP) correlation functional violates it. We extend this idea to the next generation of density functionals, those which incorporate exact exchange via the optimized effective potential (OEP), with a model in which the correlation hole is constructed from the exact exchange hole. The resulting exchange-correlation hole is deeper and less diffuse than the exact exchange hole. We denote such a functional as \textquoteleft\textquoteleftlocally correlated Hartree-Fock\textquoteright\textquoteright and list a variety of conditions such a functional should satisfy. We demonstrate the promise of this approach with a crude simple model. \copyright 1997 John Wiley & Sons, Inc.
Reference:
Why the generalized gradient approximation works and how to go beyond it Kieron Burke, John P. Perdew and Ernzerhof, Matthias, International Journal of Quantum Chemistry 61, 287-293 (1997).
Bibtex Entry:
@article{BPE97,
Pub-num = {023},
Abstract = {Abstract The local spin density (LSD) approximation, while of only moderate accuracy, has proven extremely reliable over three decades of use. We argue that any gradient-corrected functional should preserve the correct features of LSD even if the system under study contains no regions of small density gradient. The Perdew-Wang 1991 (PW91) functional respects this condition, while, e.g., the Lee-Yang-Parr (LYP) correlation functional violates it. We extend this idea to the next generation of density functionals, those which incorporate exact exchange via the optimized effective potential (OEP), with a model in which the correlation hole is constructed from the exact exchange hole. The resulting exchange-correlation hole is deeper and less diffuse than the exact exchange hole. We denote such a functional as {\textquoteleft}{\textquoteleft}locally correlated Hartree-Fock{\textquoteright}{\textquoteright} and list a variety of conditions such a functional should satisfy. We demonstrate the promise of this approach with a crude simple model. {\copyright} 1997 John Wiley \& Sons, Inc.},
Author = {Kieron Burke and John P. Perdew and Ernzerhof, Matthias},
Date-Modified = {2013-02-12 00:16:04 +0000},
Doi = {10.1002/(SICI)1097-461X(1997)61:2<287::AID-QUA11>3.0.CO;2-9},
Issn = {1097-461X},
Journal = {International Journal of Quantum Chemistry},
Number = {2},
Pages = {287-293},
Publisher = {John Wiley \& Sons, Inc.},
Title = {Why the generalized gradient approximation works and how to go beyond it},
Url = {http://dx.doi.org/10.1002/(SICI)1097-461X(1997)61:2<287::AID-QUA11>3.0.CO;2-9},
Volume = {61},
Year = {1997},
Bdsk-Url-1 = {http://dx.doi.org/10.1002/(SICI)1097-461X(1997)61:2%3C287::AID-QUA11%3E3.0.CO;2-9}}