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Excited state geometries within time-dependent and restricted open-shell density functional theories


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.

Abstract

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.

Abstract

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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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Uncontrolled Keywords:Excitation energies; Density functional theory; Molecular dynamics
Language:English
Date:July 2003
Deposited On:18 Mar 2009 14:50
Last Modified:05 Apr 2016 12:26
Publisher:Elsevier
ISSN:0166-1280
Publisher DOI:https://doi.org/10.1016/S0166-1280(03)00152-0

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