External orthogonality in subsystem time-dependent density functional theory. Issue 31 (2nd March 2016)

• Record Type: Journal Article
• Authors: Chulhai, Dhabih V.; Jensen, Lasse
• Is Part Of: Physical chemistry chemical physics. Volume 18:Issue 31(2016)
• Page Start: 21032
• Page End: 21039
• Publication Date: 2016-03-02
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c6cp00310a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : We present a subsystem TDDFT method which maintains inter-subsystem orbital orthogonality. 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).