4.6 Article

External orthogonality in subsystem time-dependent density functional theory

期刊

PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 18, 期 31, 页码 21032-21039

出版社

ROYAL SOC CHEMISTRY
DOI: 10.1039/c6cp00310a

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资金

  1. NSF [CHE-1362825]
  2. Research Computing and Cyberinfrastructure, a unit of Information Technology Services at Penn State
  3. Division Of Chemistry
  4. Direct For Mathematical & Physical Scien [1362825] Funding Source: National Science Foundation

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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).

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