All-electron four-component Dirac-Kohn-Sham procedure for large molecules and clusters containing heavy elements

Abstract

In exploiting state-of-the-art density fitting algorithms, we show that relativistic four-component Dirac-Kohn-Sham computations using G -spinor basis sets and Hermite Gaussian fitting functions can readily be applied to large molecular systems, including large clusters of heavy atoms. The inherent accuracy of the fitting procedure is discussed and the techniques to ensure high accuracy are mentioned. The power of the method, with its reduced scaling with respect to size and a prefactor shrunk by several orders of magnitude, is illustrated through some all-electron test calculations on gold clusters up to Au16. © 2008 The American Physical Society.