Three-Center Tight-Binding Together with Multipolar Auxiliary Functions

We present an ab initio tight-binding method that allows to improve on the effective potential and minimal basis approximations employed in semiempirical calculations. Three-center expansions are used to evaluate the zeroth-order Hamiltonian matrix elements and repulsive energy terms in the spirit of the Horsfield method. Self-consistency is handled by expanding atomic orbital products in an auxiliary basis following the work of Giese and York, combined with a two-center expansion of the exchange–correlation kernels. Together with nonminimal main basis sets (double-ζ plus polarization), we show that the resulting method trades a modest amount of accuracy for a significant gain in speed, compared to that of numerical atomic orbital density functional theory, in calculations on small molecules, bulk compounds, and metal nanoclusters.