Molecular modeling annual

, Volume 8, Issue 3, pp 87–94 | Cite as

Excited state conformational dynamics of semiflexibly bridged electron donor-acceptor systems: a semiempirical CI-study including solvent effects

  • Timothy Clark
  • Bernd Bleisteiner
  • Siegfried Schneider
Original Paper

Abstract.

Semiempirical (AM1) molecular orbital theory with configuration interaction has been used to investigate the harpooning mechanism proposed from experimental studies on semiflexibly bridged electron donor-acceptor systems. Our calculations on the charge-transfer state of N-phenyl-4-(4-cyano-naphth-1-ylmethyl)-piperidine, 1, confirm the proposed harpooning mechanism including an intermediate loosely folded charge-transfer state and reproduce the thermodynamics obtained from our spectroscopic studies closely. The structural details of the extended (ECT), intermediate (ICT) and compact (CCT) charge-transfer states are discussed, as are the transition states connecting them. Solvent effects have been modeled using self-consistent reaction field (SCRF) calculations within the polarized continuum model. The effect of solvent polarity on the stabilities of the three charge-transfer states is discussed.

Keywords Semiempirical MO-theory AM1 Excited states Charge transfer Solvation 

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Copyright information

© Springer-Verlag 2002

Authors and Affiliations

  • Timothy Clark
    • 1
  • Bernd Bleisteiner
    • 2
  • Siegfried Schneider
    • 2
  1. 1.Computer-Chemie-Centrum der Universität Erlangen-Nürnberg, Nägelsbachstraße 25, 91054 Erlangen, Germany Clark@chemie.uni-erlangen.deDE
  2. 2.Institut für Physikalische und Theoretische Chemie der Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, GermanyDE

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