title: Conductor-like screening model for relaxed excited states: Implementation in the semiempirical method MSINDO.
abstract: Two approaches to treat solvent polarization and reorientation effects for excited states of molecules and surfaces have been implemented in the recently developed MSINDO-sCIS method (Gadaczek, Krause, Hintze, Bredow, J. Chem. Theory Comput. 2011, 7, 3675). They allow for an efficient calculation of analytical energy gradients and hence open the opportunity to investigate fluorescence effects or photochemical reactions in solution for large molecules that are difficult to treat with high-level methods. Both approaches are based on the conductor-like screening model (COSMO) (Klamt and Schüürmann, J. Chem. Soc., Perkin Trans. 1993, 2, 799) in combination with the configuration interaction singles (CIS) method (Foresman, Head-Gordon, Pople, and Frisch, J. Phys. Chem. 1992, 96, 135). The paper gives a brief outline of the theoretical background. As a first application, solvent shifts of three well-studied, environment-sensitive fluorescent dyes (Kucherak, Didier, Mély, and Klymchenko, J. Phys. Chem. Lett. 2010, 1, 616) have been calculated and compared with experimental results and standard time-dependent density functional theory. A statistical evaluation of MSINDO-COSMO-sCIS is provided for a set of 39 molecules suggested recently by Jacquemin et al. (Jacquemin, Planchat, Adamo, and Mennucci, J. Chem. Theory Comput. 2012, 8, 2359). Calculated vertical and adiabatic excitation energies and fluorescence energies are compared to experimental data.
authors.affiliation: Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Beringstr. 4, 53115, Bonn, Germany; Karlsruhe Institute of Technology (KIT), Institute of Physical Chemistry, Theoretical Chemistry Group, KIT Campus South, P. O. Box 6980, 76049, Karlsruhe, Germany.
authors.forename: Katharina
authors.initials: K
authors.lastname: Krause
authors.forename: Thomas
authors.initials: T
authors.lastname: Bredow
mesh_terms: D000465:Algorithms; D005453:Fluorescence; D005456:Fluorescent Dyes / Q000737:chemistry*; D008956:Models, Chemical; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry
chemical_list: D005456:Fluorescent Dyes; D012997:Solvents
keywords: analytic gradients; conductor-like screening model; configuration interaction singles; excited states; semiempirical methods