title: Charge transfer, double and bond-breaking excitations with time-dependent density matrix functional theory.
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.
authors.affiliation: Afdeling Theoretische Chemie, Vrije Universiteit, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
authors.forename: K J H
authors.initials: KJ
authors.lastname: Giesbertz
authors.forename: E J
authors.initials: EJ
authors.lastname: Baerends
authors.forename: O V
authors.initials: OV
authors.lastname: Gritsenko