Projector Augmented Wave Method Incorporated into Gauss-Type Atomic Orbital Based Density Functional Theory

摘要

The Projector Augmented Wave (PAW) method developed by Blochl is well recognized as an efficient, accurate pseudopotential approach in solid-state density functional theory (DFT) calculations with the plane-wave basis. Here we present an approach to incorporate the PAW method into the Gauss-type function (GTF) based DFT implementation, which is widely used for molecular quantum chemistry calculations. The nodal and high-exponent GTF components of valence molecular orbitals (MOs) are removed or pseudized by the ultrasoft PAW treatment, while there is elaborate transparency to construct an accurate and well-controlled pseudopotential from all-electron atomic description and to reconstruct an all-electron form of valence MOs from the pseudo MOs. The smoothness of the pseudo MOs should benefit the efficiency of GTF-based DFT calculations in terms of elimination of high-exponent primitive GTFs and reduction of grid points in the numerical quadrature. The processes of the PAW method are divided into basis-independent and -dependent parts. The former is carried out using the previously developed PAW libraries LIBPAW and ATOMPAW. The present scheme is implemented by incorporating LIBPAW into the conventional GTF-based DFT solver. The details of the formulations and implementations of GTF-related PAW procedures are presented. The test calculations are shown for illustrating the performance. With the near-complete GTF basis at the cc-pVQZ level, the total energies obtained using our PAW method with suited frozen core treatments converge to those with the conventional all-electron GTF-based method with a rather small absolute error.