The limitations of Slater's element-dependent exchange functional from analytic density functional theory

Details The limitations of Slater's element-dependent exchange functional from analytic density functional theory The limitations of Slater's element-dependent exchange functional from analytic density functional theory

2005-11-25

arxiv.org/abs/cond-mat/0511635v1

Physics

Condensed Matter

Other Condensed Matter

33 pages, Uses RevTex, to appear in The Journal of Chemical Physics

Scientific paper

10.1063/1.2161176

Our recent formulation of the analytic and variational Slater-Roothaan (SR) method, which uses Gaussian basis sets to variationally express the molecular orbitals, electron density and the one body effective potential of density functional theory, is reviewed. Variational fitting can be extended to the resolution of identity method,where variationality then refers to the error in each two electron integral and not to the total energy. It is proposed that the appropriate fitting functions be charge neutral and that all ab initio energies be evaluated using two-center fits of the two-electron integrals. The SR method has its root in the Slater's Xalpha method and permits an arbitrary scaling of the Slater-Gaspar-Kohn-Sham exchange-correlation potential around each atom in the system. Of several ways of choosing the scaling factors (Slater's exchange parameters), two most obvious are the Hartree-Fock (HF), alpha_HF, values and the exact atomic, alpha_EA, values. The performance of this simple analytic model with both sets for atomization energies of G2 set of 148 molecules is better than the local density approximation or the HF theory, although the errors in atomization energy are larger than the target chemical accuracy. To improve peformance for atomization energies, the SR method is reparametrized to give atomization energies of 148 molecules to be comparbale to those obtained by one of the most widely used generalized gradient approximations. The mean absolute error in ionization potentials of 49 atoms and molecules is about 0.5 eV and that in bond distances of 27 molecules is about 0.02 Angstrom. The overall good performance of the computationally efficient SR method using any reasonable set of alpha values makes it a promising method for study of large systems.

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