Recent Advances in Cartesian-Grid DFT in Atoms and Molecules

Abstract

In the past several decades, density functional theory (DFT) has evolved as a leading player across a dazzling variety of fields, from organic chemistry to condensed matter physics. The simple conceptual framework and computational elegance are the underlying driver for this. This article reviews some of the recent developments that have taken place in our laboratory in the past 5 years. Efforts are made to validate a viable alternative for DFT calculations for small to medium systems through a Cartesian coordinate grid- (CCG-) based pseudopotential Kohn–Sham (KS) DFT framework using LCAO-MO ansatz. In order to legitimize its suitability and efficacy, at first, electric response properties, such as dipole moment (μ), static dipole polarizability (α), and first hyperpolarizability (β), are calculated. Next, we present a purely numerical approach in CCG for proficient computation of exact exchange density contribution in certain types of orbital-dependent density functionals. A Fourier convolution theorem combined with a range-separated Coulomb interaction kernel is invoked. This takes motivation from a semi-numerical algorithm, where the rate-deciding factor is the evaluation of electrostatic potential. Its success further leads to a systematic self-consistent approach from first principles, which is desirable in the development of optimally tuned range-separated hybrid and hyper functionals. Next, we discuss a simple, alternative time-independent DFT procedure, for computation of single-particle excitation energies, by means of “adiabatic connection theorem” and virial theorem. Optical gaps in organic chromophores, dyes, linear/non-linear PAHs, and charge transfer complexes are faithfully reproduced. In short, CCG-DFT is shown to be a successful route for various practical applications in electronic systems.