Correlation energy functionals dependent on an effective number of electrons: Charged species and equilibrium geometries

摘要

Recently proposed spin-dependent and spin-independent correlation energy functionals [Perez-Jimenez , J. Chem. Phys. 116, 10571 (2002)] based on an effective number of electrons N are extended to deal with charged systems. By introducing the concept of an effective atomic number Z analogous to N, the spin-dependent functional in combination with Becke's exchange [Becke, Phys. Rev. A 38, 3098 (1988)] yields a mean absolute error (MAE) of 5.4 kcal/mol for the 88 ionization potentials and 58 electron affinities included in the extended G2 set, and a MAE of 4.1 kcal/mol for the 312 data comprising the above plus the 148 enthalpies of formation of the extended G2 set and the 18 total energies of the neutral atoms H through Ar. Geometry optimizations performed on the 53 molecules of the G2-1 test set with the above combination of exchange and correlation functionals yield MAEs of 0.017 A and 1.5 degrees for the 68 bond lengths and 29 angles analyzed as compared with the experimental estimates. (c) 2005 American Institute Physics.