Numerical Fitting of Molecular Properties to Hermite Gaussians

摘要

A procedure is presented to fit gridded molecular properties to auxiliary basis sets (ABSs) of Hermite Gaussians, analogous to the density fitting (DF) method (Dunlap; et al. J. Chem. Phys. >1979, 71, 4993). In this procedure, the ab initio calculated properties (density, electrostatic potential, and/or electric field) are fitted via a linear- or nonlinear-least-squares procedure to auxiliary basis sets (ABS). The calculated fitting coefficients from the numerical grids are shown to be more robust than analytic density fitting due to the neglect of the core contributions. The fitting coefficients are tested by calculating intermolecular Coulomb and exchange interactions for a set of dimers. It is shown that the numerical instabilities observed in DF are caused by the attempt of the ABS to fit the core contributions. In addition, this new approach allows us to reduce the number of functions required to obtain an accurate fit. This results in decreased computational cost, which is shown by calculating the Coulomb energy of a 4096 water box in periodic boundary conditions. Using atom centered Hermite Gaussians, this calculation is only 1 order of magnitude slower than conventional atom–centered point charges.