Charge transfer, double and bond-breaking excitations with time-dependent density matrix functional theory

K.J.H. Giesbertz, E.J. Baerends, O.V. Gritsenko

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Abstract

Time-dependent density functional theory (TDDFT) in its current adiabatic implementations exhibits three remarkable failures: (a) completely wrong behavior of the excited state surface along a bond-breaking coordinate; (b) lack of doubly excited configurations; (c) much too low charge transfer excitation energies. These TDDFT failure cases are all strikingly exhibited by prototype two-electron systems such as dissociating H2 and HeH+. We find for these systems with time-dependent density matrix functional theory that: (a) Within previously formulated simple adiabatic approximations, the bonding-to- antibonding excited state surface as well as charge transfer excitations are described without problems, but not the double excitations; (b) An adiabatic approximation is formulated in which also the double excitations are fully accounted for. © 2008 The American Physical Society.
Original languageEnglish
Pages (from-to)033004
JournalPhysical Review Letters
Volume101
Issue number3
DOIs
Publication statusPublished - 2008

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