Interpolative Separable Density Fitting through Centroidal Voronoi Tessellation With Applications to Hybrid Functional Electronic Structure Calculations.

The recently developed interpolative separable density fitting (ISDF) decomposition is a powerful way for compressing the redundant information in the set of orbital pairs and has been used to accelerate quantum chemistry calculations in a number of contexts. The key ingredient of the ISDF decomposition is to select a set of nonuniform grid points, so that the values of the orbital pairs evaluated at such grid points can be used to accurately interpolate those evaluated at all grid points. The set of nonuniform grid points, called the interpolation points, can be automatically selected by a QR factorization with column pivoting (QRCP) procedure. This is the computationally most expensive step in the construction of the ISDF decomposition. In this work, we propose a new approach to find the interpolation points based on the centroidal Voronoi tessellation (CVT) method, which offers a much less expensive alternative to the QRCP procedure when ISDF is used in the context of hybrid functional electronic structure calculations. The CVT method only uses information from the electron density and can be efficiently implemented using a K-Means algorithm. We find that this new method achieves comparable accuracy to the ISDF-QRCP method, at a cost that is negligible in the overall hybrid functional calculations. For instance, for a system containing 1000 silicon atoms simulated using the HSE06 hybrid functional on 2000 computational cores, the cost of the QRCP-based method for finding the interpolation points is 38.1 s, while the CVT procedure only takes 0.7 s. We also find that the ISDF-CVT method enhances the smoothness of the potential energy surface in the context of ab initio molecular dynamics (AIMD) simulations with hybrid functionals.