title: Vibrationally resolved UV/Vis spectroscopy with time-dependent density functional based tight binding.
abstract: We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon method with a harmonic approximation for the nuclear wavefunction. The theory of vibrationally resolved UV/Vis spectroscopy is first summarized from the viewpoint of TD-DFTB. The method is benchmarked against time-dependent density functional theory (TD-DFT) calculations for strongly dipole allowed excitations in various aromatic and polar molecules. Using the recent 3ob:freq parameter set of Elstner's group, very good agreement with TD-DFT calculations using local functionals was achieved.
authors.affiliation: Scientific Computing and Modelling NV, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
authors.forename: Robert
authors.initials: R
authors.lastname: Rüger
authors.affiliation: Univ Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière, F-69622 Villeurbanne, France.
authors.forename: Thomas
authors.initials: T
authors.lastname: Niehaus
authors.affiliation: Scientific Computing and Modelling NV, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
authors.forename: Erik
authors.initials: E
authors.lastname: van Lenthe
authors.affiliation: Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Linnéstr. 2, 04103 Leipzig, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Heine
authors.affiliation: Department of Theoretical Chemistry, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
authors.forename: Lucas
authors.initials: L
authors.lastname: Visscher