Permanent URL to this publication: http://dx.doi.org/10.5167/uzh-3189
Odelius, M; Laikov, D; Hutter, J (2003). Excited state geometries within time-dependent and restricted open-shell density functional theories. Journal of Molecular Structure THEOCHEM, 630(1-3):163-175.
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Singlet excited state geometries of a set of medium sized molecules with different characteristic lowest excitations are studied. Geometry optimizations of excited states are performed with two closely related restricted open-shell Kohn-Sham methods and within linear response to time-dependent density functional theory. The results are compared to wave-function based methods. Excitation energies (vertical and adiabatic) calculated from the open-shell methods show systematic errors depending on the type of excitation. However, for all states accessible by the restricted methods a good agreement for the geometries with time-dependent density functional theory and wave-function based methods is found. An analysis of the energy with respect to the mixing angle for the singly occupied orbitals reveals that some states (mostly n --> pi]) are stable when symmetry constraints are relaxed and others (mostly [pi --> pi]) are instable. This has major implications on the applicability of the restricted open-shell methods in molecular dynamics simulations.
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|Item Type:||Journal Article, refereed, original work|
|Communities & Collections:||07 Faculty of Science > Department of Chemistry|
|Uncontrolled Keywords:||Excitation energies; Density functional theory; Molecular dynamics|
|Deposited On:||18 Mar 2009 14:50|
|Last Modified:||05 Jun 2014 13:52|
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