External orthogonality in subsystem time-dependent density functional theory

Dhabih V. Chulhai, Lasse Jensen

Research output: Contribution to journalArticle

13 Citations (Scopus)

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).

Original languageEnglish (US)
Pages (from-to)21032-21039
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume18
Issue number31
DOIs
StatePublished - Jan 1 2016

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orthogonality
Discrete Fourier transforms
Kinetic energy
Density functional theory
kinetic energy
density functional theory
flux density
approximation
Molecular orbitals
molecular orbitals

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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External orthogonality in subsystem time-dependent density functional theory. / Chulhai, Dhabih V.; Jensen, Lasse.

In: Physical Chemistry Chemical Physics, Vol. 18, No. 31, 01.01.2016, p. 21032-21039.

Research output: Contribution to journalArticle

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