Excitation energies with time-dependent density matrix functional theory: Singlet two-electron systems

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

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Abstract

Time-dependent density functional theory in its current adiabatic implementations exhibits three striking failures: (a) Totally wrong behavior of the excited state surface along a bond-breaking coordinate, (b) lack of doubly excited configurations, affecting again excited state surfaces, and (c) much too low charge transfer excitation energies. We address these problems with time-dependent density matrix functional theory (TDDMFT). For two-electron systems the exact exchange-correlation functional is known in DMFT, hence exact response equations can be formulated. This affords a study of the performance of TDDMFT in the TDDFT failure cases mentioned (which are all strikingly exhibited by prototype two-electron systems such as dissociating H2 and HeH
Original languageEnglish
Pages (from-to)114104
JournalJournal of Chemical Physics
Volume130
Issue number11
DOIs
Publication statusPublished - 2009

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