Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

As previously shown [M. Levy and J. P. Perdew, Phys. Rev. A (in press)], the customary Hohenberg–Kohn density functional, based on the universal functional F[ ρ], does not exhibit naively expected scaling properties. Namely, if ρλ=λ3ρ(λr) is the scaled density corresponding to ρ(r), the expected scaling, not satisfied, is T[ρλ]=λ2T[ρ] and V[ρλ]=λV[ρ], where T and V are the kinetic and potential energy components. By defining a new functional of ρ and λ, F[ ρ, λ], it is now shown how the naive scaling can be preserved. The definition is F[ρ(r), λ]=〈λ3N/2 Φminρλ (λr1... λrN)|T̂(r1...rN) +Vee(r1...rN)| λ3N/2Φminρλ(λr1...λrN)〉, where λ3N/2 Φminρλ(λr1... λrN) is that antisymmetric function Φ which yields ρλ(r)=λ3ρ(λr) and simultaneously minimizes 〈Φ|T̂(r1...rN) +λVee(r1...rN)|Φ〉. The corresponding variational principle is EvG.S.=Infλ, ρ(r){∫  drv(r) ρλ(r)+λ2T[ ρ(r)] +λVee[ ρ(r)]}, where EvG.S. is the ground-state energy for potential v(r). One is thus allowed to satisfy the virial theorem by optimum scaling just as if the naive scaling relations were correct for F[ ρ].

Bibliography

Levy, M., Yang, W., & Parr, R. G. (1985). A new functional with homogeneous coordinate scaling in density functional theory: F [ ρ,λ]. The Journal of Chemical Physics, 83(5), 2334–2336.

Authors 3
  1. Mel Levy (first)
  2. Weitao Yang (additional)
  3. Robert G. Parr (additional)
References 8 Referenced 45
  1. 10.1103/PhysRevA.1.969 / Phys. Rev. A (1970)
  2. 10.1515/zna-1975-1203 / Z. Naturforsch. Teil A (1975)
  3. 10.1103/PhysRevB.24.6795 / Phys. Rev. B (1981)
  4. 10.1063/1.448229 / J. Chem. Phys. (1985)
  5. {'key': '2024021002251350400_r5'}
  6. 10.1073/pnas.76.12.6062 / Proc. Natl. Acad. Sci. U.S.A. (1979)
  7. {'key': '2024021002251350400_r6a'}
  8. {'key': '2024021002251350400_r7'}
Dates
Type When
Created 23 years, 1 month ago (July 26, 2002, 9 a.m.)
Deposited 1 year, 6 months ago (Feb. 9, 2024, 10:44 p.m.)
Indexed 4 weeks, 2 days ago (Aug. 2, 2025, 1:05 a.m.)
Issued 40 years ago (Sept. 1, 1985)
Published 40 years ago (Sept. 1, 1985)
Published Print 40 years ago (Sept. 1, 1985)
Funders 0

None

@article{Levy_1985, title={A new functional with homogeneous coordinate scaling in density functional theory: F [ ρ,λ]}, volume={83}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.449326}, DOI={10.1063/1.449326}, number={5}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Levy, Mel and Yang, Weitao and Parr, Robert G.}, year={1985}, month=sep, pages={2334–2336} }