On the large‐gradient behavior of the density functional exchange energy

A coordinate‐space model of the exchange hole density, previously introduced by the author, is extrapolated to the case of very strongly inhomogeneous systems (i.e., large density gradients). As a result, we propose a new gradient‐corrected exchange energy functional for application to atomic and molecular problems. The model provides theoretical estimates of the parameters in the functional, and these compare well with empirical values deduced from a least squares fit to exact atomic data.

[1]  P. Marcus,et al.  Computational methods in band theory , 1971 .

[2]  Axel D. Becke,et al.  Density Functional Calculations of Molecular Bond Energies , 1986 .

[3]  Exchange density-functional gradient expansion , 1984 .

[4]  A. Voros,et al.  Semiclassical approximations for nuclear hamiltonians. I. Spin-independent potentials , 1979 .

[5]  John C. Slater,et al.  The self-consistent field for molecules and solids , 1974 .

[6]  F. W. Averill,et al.  Bonding in the first-row diatomic molecules within the local spin-density approximation , 1982 .

[7]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[8]  Axel D. Becke,et al.  Local exchange-correlation approximations and first-row molecular dissociation energies , 1985 .

[9]  Axel D. Becke,et al.  Hartree–Fock exchange energy of an inhomogeneous electron gas , 1983 .

[10]  J. Perdew,et al.  Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation. , 1986, Physical review. B, Condensed matter.

[11]  D. Langreth,et al.  Beyond the local-density approximation in calculations of ground-state electronic properties , 1983 .

[12]  Frank Herman,et al.  Improved Statistical Exchange Approximation for Inhomogeneous Many-Electron Systems , 1969 .

[13]  J. Perdew,et al.  Accurate density functional for the energy: Real-space cutoff of the gradient expansion for the exchange hole. , 1985, Physical review letters.

[14]  K. Schwarz.  A study of the Xαβ-exchange approximation on atoms for use in molecular and solid-state calculations , 1975 .