Generalized gradient approximation for the exchange-correlation hole of a many-electron system

[摘要] We construct a generalized gradient approximation (GGA) for the density n(xc)(r,r+u) at position r+u of the exchange-correlation hole surrounding an electron at r, or more precisely for its system and spherical average [n(xc)(u)]=(4 pi)(-1)integral d Omega(u)N(-1)integral d(3)r n(r)n(xc)(r,r+u). Starting from the second-order density gradient expansion, which involves the local spin densities n(up arrow)(r),n(down arrow)(r) and their gradients del n(up arrow)(r), del n(down arrow)(r), we cut off the spurious large-u contributions to restore those exact conditions on the hole that the local spin density (LSD) approximation respects. Our GGA hole recovers the Perdew-Wang 1991 and Perdew-Burke-Ernzerhof GGA's for the exchange-correlation energy, which therefore respect the same powerful hole constraints as LSD. When applied to real systems, our hole model provides a more detailed test of these energy functionals, and also predicts the observable electron-electron structure factor.

[关键词] DENSITY-FUNCTIONAL THERMOCHEMISTRY;GAS CORRELATION-ENERGY;STRUCTURAL-PROPERTIES;LOCAL-DENSITY;SOLIDS;TRANSITION;EXPANSION;ACCURATE;METALS;POTENTIALS