Expansions of the correlation-energy density functional E(c)[rho] and its kinetic-energy component T-c[rho] in terms of homogeneous functionals

被引:106
作者
Liu, SB
Parr, RG
机构
[1] Department of Chemistry, University of North Carolina, Chapel Hill, NC
来源
PHYSICAL REVIEW A | 1996年 / 53卷 / 04期
关键词
D O I
10.1103/PhysRevA.53.2211
中图分类号
O43 [光学];
学科分类号
070207 ; 0803 ;
摘要
Based on the constrained-search formulation of a coupled Hamiltonian, new formulas are given involving the correlation-energy density functional E(c)[rho] and its kinetic component T-c[rho], starting from two relations of Levy and Perdew. Consequences are examined of assuming (following earlier authors) the existence of a Taylor series expansion of E(c)(lambda)[rho] in the coupling parameter lambda. If one truncates the series at the linear term, one finds that E(c)[rho] and T-c[rho] are homogeneous of degree zero with respect to coordinate scaling, and if local, they are homogeneous of degree one in the density scaling. More generally, it is shown that E(c)[rho] and T-c[rho] are linear combinations of homogeneous functionals of different specific degrees in coordinate scaling: 0,-1,-2, -3,...,(1-n),.... If the functionals also are local, both E(c)[rho] and T-c[rho] are combinations of functionals [rho(k)] homogeneous in rho of degrees k=1,2/3,1/3,0,...,(4-n)/3,.... For atoms and molecules, k greater than or equal to 0, and so E(c) and T-c take the form X(c)[rho]=aN+bf rho(2/3)(r)d(3)r+cf rho(1/3)(r)d(3)r+d, where a, b, c, and d are constants to be determined. Numerical tests are given that demonstrate the effectiveness of such series of local functionals. We also give definitions of density scaling, coordinate scaling, and homogeneities, and relations among them.
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页码:2211 / 2219
页数:9
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