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Non-Adiabatic Photoprocesses of Fundamental Importance to Chemistry: From Electronic Relaxation of DNA Bases to Intramolecular Charge Transfer in Electron Donor-Acceptor Molecules

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Radiation Induced Molecular Phenomena in Nucleic Acids

Part of the book series: Challenges and Advances In Computational Chemistry and Physics ((COCH,volume 5))

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Abstract

Substituent effects on ultrafast electronic relaxation (internal conversion) of nucleobases and intramolecular charge transfer in electron donor-acceptor (EDA) molecules, containing benzonitrile and diphenylacetylene moieties, have been investigated using laser spectroscopy and simple ab initio methods. The results demonstrate the central role biradical states play in the nonadiabatic energy- and charge-transfer dynamics. Specifically, subpicosecond internal conversion characteristic of the naturally occurring nucleobases is effectively extinguished by covalent modification that prevents the out-of-plane deformation of the π π* singlet state into the twisted ethene-like structure of the biradical state. Similarly, the covalently modified EDA molecules, in which the biradical (π σ*) state of bent geometry lies substantially above the optically prepared ππ* state, do not exhibit intramolecular charge transfer even in highly polar solvents

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Author information

Authors and Affiliations

  1. Steacie Institute for Molecular Science, National Research Council of Canada, Ottawa, K1A 0R6, Canada

    Marek Z. Zgierski

  2. Department of Chemistry and the Center for Laser and Optical Spectroscopy, The University of Akron, Akron, OH 44325-3601, USA

    Takashige Fujiwara & Edward C. Lim

Authors
  1. Marek Z. Zgierski
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  2. Takashige Fujiwara
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  3. Edward C. Lim
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Editor information

Editors and Affiliations

  1. Department of Chemistry, Jackson State University, 1325 J. R. Lynch Street, Jackson, MS 39217, USA

    Manoj K. Shukla  & Jerzy Leszczynski  & 

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Zgierski, M.Z., Fujiwara, T., Lim, E.C. (2008). Non-Adiabatic Photoprocesses of Fundamental Importance to Chemistry: From Electronic Relaxation of DNA Bases to Intramolecular Charge Transfer in Electron Donor-Acceptor Molecules. In: Shukla, M.K., Leszczynski, J. (eds) Radiation Induced Molecular Phenomena in Nucleic Acids. Challenges and Advances In Computational Chemistry and Physics, vol 5. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8184-2_15

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