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Theoretical Studies of Thymine–Thymine Photodimerization: Using Ground State Dynamics to Model Photoreaction

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Practical Aspects of Computational Chemistry I

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Abstract

Excited electronic states of DNA are extremely important in biology and yet most of these states have lifetimes of ∼ 1 ps. This short lifetime allows for very little nuclear rearrangement during dissipation. In particular, photoinduced thymine-thymine (TT) dimer formation has been found to be a picosecond process. The most prevalent TT dimer is formed by a [2+2] addition of the C5–C6 double bonds of the dimerizing thymines. Given the topochemical rules known for photoinduced [2+2] addition of organic compounds in the solid state, a similar set of rules is presented for TT dimerization in solution phase DNA. It is found that a single ground state geometric parameter (the distance, d,between the C5–C6 double bonds) is sufficient as a constraint on when dimers can form such that accurate TT dimer quantum yields can be predicted. The electronic basis of such a model is examined along with calibration of the model for dT20 and dA20dT20. The application and validity of this model to a variety of double and single stranded DNA systems is then discussed.

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Acknowledgements

The authors would like to thank Fred Lewis, Mahesh Hariharan and Zhengzheng Pan for performing almost all of the experiments referred to in this chapter and numerous useful discussions. Funding for this research was provided by the National Science Foundation (NSF-CRC Grant CHE-0628130).

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Authors and Affiliations

  1. Department of Chemistry, Northwestern University, Evanston, IL, 60208-3113, USA

    Martin McCullagh & George C. Schatz

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  1. Martin McCullagh
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  2. George C. Schatz
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Correspondence to George C. Schatz .

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Editors and Affiliations

  1. Department of Chemistry, Jackson State University, 17910, P.O. Box 17910, 1400 Lynch St., Jackson, 39217, Mississippi, USA

    Jerzy Leszczynski

  2. Dept. Chemistry, Jackson State University, J. R. Lynch St. 1325, Jackson, 39217, Mississippi, USA

    Manoj K. K. Shukla

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McCullagh, M., Schatz, G.C. (2011). Theoretical Studies of Thymine–Thymine Photodimerization: Using Ground State Dynamics to Model Photoreaction. In: Leszczynski, J., Shukla, M.K. (eds) Practical Aspects of Computational Chemistry I. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-0919-5_13

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