Journal of Chemical Physics, Vol.109, No.6, 2092-2098, 1998
A new inhomogeneity parameter in density-functional theory
Density-functional exchange-correlation approximations depending on spin densities and their gradients have proven remarkably accurate in recent thermochemical tests [e.g., A. D. Becke, J. Chem. Phys. 107, 8554 (1997)]. With the inherent limitations of first-order gradient corrections now in sight, however, we investigate here a class of inhomogeneity corrections based on a new second-order gradient parameter. The new parameter is logically motivated by previous work on Taylor expanded exchange hole densities, and generates exchange-correlation functionals more accurate than those containing first-order gradients only.
Keywords:COORDINATE-SPACE MODEL;CORRELATION ENERGIES;ELECTRON-GAS;EXCHANGE-ENERGY;HARTREE-FOCK;GROUND-STATE;APPROXIMATION;THERMOCHEMISTRY;MOLECULES;FORMALISM