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Ultrafast [2 + 2]-cycloaddition in norbornadiene

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Abstract

Excitation of norbornadiene (bicyclo[2.2.1]hepta-2,5-diene) at 200 nm populates two states in parallel, the second ππ* state and a Rydberg state. We monitored both populations by transient nonresonant ionization. From the ππ* state the molecule relaxes in consecutive steps with time constants 5, 31 and 55 fs down to the ground-state surface, whereas the Rydberg population merges to the other path on the ππ* surface within 420 fs. The relaxation steps are discussed in terms of conical intersections (CoIns) between different surfaces. Information on them is inferred from known spectroscopy and, for the last CoIn, from published calculations on Dewar benzene→prismane conversion and on ethylene photodimerization for which norbornadiene with its two nonconjugated double bonds is a model. The calculation predicts symmetry breaking for this CoIn, the two ethylenes forming a rhombus. Although this distortion is hindered in norbornadiene by ring strain, this CoIn seems easily accessible as indicated by the short time (<55 fs) found for passing through it.

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References

  1. W. G. Dauben, R. L. Cargill, Tetrahedron, 1961, 15, 197

    Article  CAS  Google Scholar 

  2. K. Maruyama and Y. Kubo, in Organic Photochemistry, edited by W. M. Horspool and P.-S. Song, CRC Press, Boca Raton, 1995, p. 222

  3. M. Klessinger and J. Michl, Excited states and photochemistry of organic molecules, VCH, New York, 1995

    Google Scholar 

  4. F. Bernardi, M. Olivucci, M. A. Robb, Chem. Soc. Rev., 1996, 25, 321

    Article  CAS  Google Scholar 

  5. W. Fuß, P. Hering, K. L. Kompa, S. Lochbrunner, T. Schikarski, W. E. Schmid, Ber. Bunsen-Ges. Phys. Chem., 1997, 101, 500

    Article  Google Scholar 

  6. W. Fuß, S. Lochbrunner, A. M. Müller, T. Schikarski, W. E. Schmid, S. A. Trushin, Chem. Phys., 1998, 232, 161

    Article  Google Scholar 

  7. F. Bernardi, S. De, M. Olivucci, M. A. Robb, J. Am. Chem. Soc., 1990, 112, 1737

    Article  CAS  Google Scholar 

  8. F. Bernardi, M. Olivucci, M. Robb, Acc. Chem. Res., 1990, 23, 405

    Article  CAS  Google Scholar 

  9. I. J. Palmer, M. Olivucci, F. Bernardi, M. A. Robb, J. Org. Chem., 1992, 57, 5081

    Article  CAS  Google Scholar 

  10. N. Ivanoff, F. Lahmani, J. F. Delouis, J. L. Le Gouill, J. Photochem., 1973/74, 2, 199

    Article  Google Scholar 

  11. B. C. Roquitte, J. Phys. Chem., 1965, 69, 2475

    Article  CAS  Google Scholar 

  12. B. C. Roquitte, J. Am. Chem. Soc., 1963, 85, 3700

    Article  CAS  Google Scholar 

  13. X. Xing, A. Gedanken, A.-H. Sheybani, R. McDiarmid, J. Phys. Chem., 1994, 98, 8302 and references cited therein

    Article  CAS  Google Scholar 

  14. B. O. Roos, M. Merchán, R. McDiarmid, X. Xing, J. Am. Chem. Soc., 1994, 116, 5927 and references cited therein

    Article  CAS  Google Scholar 

  15. W. Fuß, S. A. Trushin, W. E. Schmid, Res. Chem. Intermed., 2001, 27, 447

    Article  Google Scholar 

  16. B. A. Horn, J. L. Herek, A. H. Zewail, J. Am. Chem. Soc., 1996, 118, 8755

    Article  CAS  Google Scholar 

  17. E. W.-G. Diau, S. De Feyter, A. H. Zewail, Chem. Phys. Lett., 1999, 304, 134

    Article  CAS  Google Scholar 

  18. R. P. Frueholz, W. F. Flicker, O. A. Mosher, A. Kuppermann, J. Chem. Phys., 1979, 70, 1986

    Article  CAS  Google Scholar 

  19. G. Bieri, F. Burger, E. Heilbronner, J. P. Maier, Helv. Chim. Acta, 1977, 60, 2213

    Article  CAS  Google Scholar 

  20. W. Fuß, W. E. Schmid, S. A. Trushin, J. Chem. Phys., 2000, 112, 8347

    Article  Google Scholar 

  21. S. A. Trushin, W. Fuß, W. E. Schmid, Phys. Chem. Chem. Phys., 2000, 2, 1435

    Article  CAS  Google Scholar 

  22. S. A. Trushin, S. Diemer, W. Fuß, K. L. Kompa, W. E. Schmid, Phys. Chem. Chem. Phys., 1999, 1, 1431

    Article  CAS  Google Scholar 

  23. W. Fuß, W. E. Schmid, S. A. Trushin, Indian Soc. Radiat. Photochem. Sci. Bull., 2000, 11, 7

    Google Scholar 

  24. S. A. Trushin, W. E. Fuß, K. K. Pushpa and W. E. Schmid, Study of ultrafast chemical dynamics by intense-laser field dissociative ionization, Minsk, Proc. SPIE, 2001, in the press

    Google Scholar 

  25. S. Meyerson, J. D. McCollum, P. N. Rylander, J. Am. Chem. Soc., 1961, 83, 1401

    Article  CAS  Google Scholar 

  26. W. Rettig, G. Wermuth, J. Photochem., 1985, 28, 351

    Article  CAS  Google Scholar 

  27. W. Fuß, Y. Haas, S. Zilberg, Chem. Phys., 2000, 259, 273

    Article  Google Scholar 

  28. G. J. Atchity, S. S. Xantheas, K. Ruedenberg, J. Chem. Phys., 1991, 95, 1862

    Article  Google Scholar 

  29. R. A. Shaw, C. Castro, R. Dutler, H. Wieser, J. Chem. Phys., 1988, 89, 716

    Article  CAS  Google Scholar 

  30. M. Garavelli, C. S. Page, P. Celani, M. Olivucci, W. E. Schmid, S. A. Trushin, W. Fuß, J. Phys. Chem. A, 2001, 105, 4458

    Article  CAS  Google Scholar 

  31. S. Wilsey, K. N. Houk, A. H. Zewail, J. Am. Chem. Soc., 1999, 121, 5772

    Article  CAS  Google Scholar 

  32. M. Rubin, J. Am. Chem. Soc., 1981, 103, 7791

    Article  CAS  Google Scholar 

  33. U. Hold, T. Lenzer, K. Luther, K. Reihs, A. Symonds, Ber. Bunsen-Ges. Phys. Chem., 1997, 101, 552

    Article  CAS  Google Scholar 

  34. Z. Li, S. L. Anderson, J. Phys. Chem. A, 1998, 102, 9202

    Article  CAS  Google Scholar 

  35. J. Benzler, S. Linkersdörfer, K. Luther, J. Chem. Phys., 1997, 106, 4992

    Article  CAS  Google Scholar 

  36. W. Fuß, W. E. Schmid, S. A. Trushin, J. Am. Chem. Soc., 2001, 123, 7101

    Article  Google Scholar 

  37. W. Fuß, K. Pushpa, W. E. Schmid, S. A. Trushin, J. Phys. Chem. A, 2001, 105, 10640

    Article  Google Scholar 

  38. R. A. Caldwell, J. Am. Chem. Soc., 1980, 102, 4004

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Max-Planck-Institut für Quantenoptik, D-85741, Garching, Germany

    Werner Fuß, Kumbil Kuttan Pushpa, Wolfram E. Schmid & Sergei A. Trushin

  2. B. I. Stepanov Institute of Physics, Belarus Academy of Sciences, 220602, Minsk, Belarus

    Sergei A. Trushin

Authors
  1. Werner Fuß
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  2. Kumbil Kuttan Pushpa
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  3. Wolfram E. Schmid
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  4. Sergei A. Trushin
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Fuß, W., Kuttan Pushpa, K., Schmid, W.E. et al. Ultrafast [2 + 2]-cycloaddition in norbornadiene. Photochem Photobiol Sci 1, 60–66 (2002). https://doi.org/10.1039/b107442c

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  • DOI: https://doi.org/10.1039/b107442c

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