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Extra info for A Different Story of pi;-Delocalizations - The Distortivity of pi;-Electrons and Its Chemical Manifestations

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Dunn, T. ; Mills, I. M. Philos. Trans. R. Soc. London 1966, A259, 499. ; Stanton, J. F. J. Phys. Chem. A 2000, 104, 2865. (b) For a refined experimental structure (neutron diffraction) see: Jeffrey, G. ; Ruble, J. ; McMullan, R. ; Pople, J. A. Proc. R. Soc. London 1987, A414, 47. (217) Krygowski, T. ; Hiberty, P. C. J. Org. Chem. 1996, 61, 8533. The authors test the σ-effect using the allperpendicular conformation of the substituents. Using this approach, our molecule 37 shows negligible positive σ-displacement.

1931, 53, 3225. (b) Pauling, L. ; Cornell University Press: Ithaca, NY, 1960. Hund, F. Z. Phys. 1927, 40, 742; 42, 93. Mulliken, R. S. Phys. Rev. 1928, 32, 186. Mulliken, R. S. Phys. Rev. 1928, 32, 761. Mulliken, R. S. Phys. Rev. 1929, 33, 730. Hu¨ckel, E. Z. Phys. 1930, 60, 423. For an interview with Hu¨ckel, in Chem. -G. J. Chem. Educ. 1972, 49, 2. See also: Berson, J. A. Chemical Creativity; WileyVCH, NY, 1999. ; Wheland, G. W. J. Chem. Phys. 1933, 1, 362. Lonsdale, K. Proc. R. Soc. London 1937, A159, 149.

1991, 95, 5524. ; Zgierski, M. Z. J. Chem. Phys. 1994, 100, 2458. The vibronic coupling effect depends on the energy gap between the zero-order states (at the geometry with uniform distances) and their coupling matrix elements. While the model reproduces the experimental results, it does not provide a clear explanation for the selectivity of the effect. ); why is the upshift effect is so strong only for the skeletal Kekule´ mode? Also, vibronic coupling is strong when the two electronic states are near each other.

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