Regensburg 2010 – wissenschaftliches Programm
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O: Fachverband Oberflächenphysik
O 78: Symposium Density functional theory and beyond for real materials
O 78.5: Hauptvortrag
Donnerstag, 25. März 2010, 17:00–17:30, H1
Excitation energies with time-dependent density matrix functional theory — •Evert Jan Baerends, Klaas J. H. Giesbertz, Oleg Gritsenko, and Katarzyna Pernal — Vrije Universiteit, Amsterdam, The Netherlands
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 [1]; b) lack of doubly excited configurations, affecting again excited state surfaces; c) much too low charge transfer excitation energies. We address these problems with time-dependent density matrix theory (TDDMFT) [2-4].
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+). At the same time, adiabatic approximations, which will eventually be necessary, can be tested without being obscured by approximations in the functional.
[1] K. J. H. Giesbertz, E. J. Baerends, Chem. Phys. Lett. 461 (2008) 338 [2] K. Pernal, O. V. Gritsenko, E. J. Baerends, Phys. Rev. A 75, 012506 (2007) [5] K. J. H. Giesbertz, E. J. Baerends, O. V. Gritsenko, Phys. Rev. Lett. 101 (2008) 033004 [6] K. J. H. Giesbertz, K. Pernal, O. V. Gritsenko, E. J. Baerends, J. Chem. Phys. 130 (2009) 114104