Issue 31, 2016

External orthogonality in subsystem time-dependent density functional theory

Abstract

Subsystem density functional theory (subsystem DFT) is a DFT partitioning method that is exact in principle, but depends on approximations to the kinetic energy density functional (KEDF). One may avoid the use of approximate KEDFs by ensuring that the inter-subsystem molecular orbitals are orthogonal, termed external orthogonality (EO). We present a method that extends a subsystem DFT method, that includes EO, into the time-dependent DFT (TDDFT) regime. This method therefore removes the need for approximations to the kinetic energy potential and kernel, and we show that it can accurately reproduce the supermolecular TDDFT results for weakly and strongly coupled subsystems, and for systems with strongly overlapping densities (where KEDF approximations traditionally fail).

Graphical abstract: External orthogonality in subsystem time-dependent density functional theory

Supplementary files

Article information

Article type
Paper
Submitted
15 Jan 2016
Accepted
25 Feb 2016
First published
25 Feb 2016

Phys. Chem. Chem. Phys., 2016,18, 21032-21039

External orthogonality in subsystem time-dependent density functional theory

D. V. Chulhai and L. Jensen, Phys. Chem. Chem. Phys., 2016, 18, 21032 DOI: 10.1039/C6CP00310A

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