Prescription for the design and selection of density functional approximations: More constraint satisfaction with fewer fits

被引:713
作者
Perdew, JP [1 ]
Ruzsinszky, A
Tao, JM
Staroverov, VN
Scuseria, GE
Csonka, GI
机构
[1] Tulane Univ, Dept Phys, New Orleans, LA 70118 USA
[2] Tulane Univ, Quantum Theory Grp, New Orleans, LA 70118 USA
[3] Rice Univ, Dept Chem, Houston, TX 77005 USA
[4] Budapest Univ Technol & Econ, Dept Inorgan Chem, H-1521 Budapest, Hungary
基金
匈牙利科学研究基金会; 美国国家科学基金会;
关键词
D O I
10.1063/1.1904565
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We present the case for the nonempirical construction of density functional approximations for the exchange-correlation energy by the traditional method of "constraint satisfaction" without fitting to data sets, and present evidence that this approach has been successful on the first three rungs of "Jacob's ladder" of density functional approximations [local spin-density approximation (LSD), generalized gradient approximation (GGA), and meta-GGA]. We expect that this approach will also prove successful on the fourth and fifth rungs (hyper-GGA or hybrid and generalized random-phase approximation). In particular, we argue for the theoretical and practical importance of recovering the correct uniform density limit, which many semiempirical functionals fail to do. Among the beyond-LSD functionals now available to users, we recommend the nonempirical Perdew-Burke-Ernzerhof (PBE) GGA and the nonempirical Tao-Perdew-Staroverov-Scuseria (TPSS) meta-GGA, and their one-parameter hybrids with exact exchange. TPSS improvement over PBE is dramatic for atomization energies of molecules and surface energies of solids, and small or moderate for other properties. TPSS is now or soon will be available in standard codes such as GAUSSIAN, TURBOMOLE, NWCHEM, ADF, WIEN, VASP, etc. We also discuss old and new ideas to eliminate the self-interaction error that plagues the functionals on the first three rungs of the ladder, bring up other related issues, and close with a list of "do's and don't's" for software developers and users. (C) 2005 American Institute of Physics.
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页数:9
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