A new parameter-free correlation functional based on an average atomic reduced density gradient analysis

摘要

A new parameter-free correlation functional based on the local Ragot-Cortona approach [J. Chem. Phys. 121, 7671 (2004)] is presented. This functional rests on a single ansatz for the gradient correction enhancement factor: it is assumed to be given by a simple analytic expression satisfying some exact conditions and containing two coefficients. These coefficients are determined without implementing the functional and without using a fitting procedure to experimental data. Their values are determined by requiring that the functional gives a correct average reduced density gradient for atoms, which, to some extent, can be considered an intrinsic atomic property. The correlation functional is then coupled with the Perdew-Burke-Erzernhof (PBE) exchange and compared with the original PBE approach as well as with some other pure density or hybrid approaches. Standard tests for atomic and molecular systems show that our new functional significantly improves on PBE, showing very interesting properties. (c) 2008 American Institute of Physics.