σ and π Electrons in Organic Compounds (Topics in Current by W. Kutzelnigg, G. Del Re, G. Berthier

By W. Kutzelnigg, G. Del Re, G. Berthier

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With the exception of semi-empirical methods based on the treatm e n t of benzene given b y Hiickel in 1931 1), all the ~ electron theories use more or less the procedure devised b y Goeppert-Mayer and Sklar ~) (henceforth abbreviated GMS) to determine the potential in which the six ~ electrons of benzene move. e. to reduce, say, the nuclear charge + 6 of carbon to + 4. g. 3)), but avoids some difficulties due to the orthogonality conditions between inner and outer orbitals. g. for the 3p~ orbitals of sulphur and phosphorus, because in those cases there are ~ orbitals in the inner shells.

84, 540 (1962). 10) Denbigh, K. : Trans. F a r a d a y Soc. 36, 936 (1940). : J. Chem. Phys. 46, 1426 (1967). 12) Wilkins, R. , Taylor, It. S. : J. Chem. Phys. 48, 4934 (1968). 13) Stevens, 1~. , Lipscomb, W. : J. Chem. Phys. 41, 184 (1964). 14) O'Hare, J. , Hurst, R. : J. Chem. Phys. 46, 2356 (1967). 16) McLean, A. , Yoshimine, M. : J. Chem. Phys. 46, 3682 (1967). is) Lefebvre, R. J. w . : Advan. Phys. Org. Chem. 3, 1 (1965). : E. Z. Physik 63, 245 (1930). 18) I)avies, P. : Trans. F a r a d a y Soc.

I, p. 206. , Jaffd, H. : J. Am. Chem. Soc. 8d, 540 (1962). Of course, the energy levels of the molecular orbitals are not identical with those of the AO's from which t h e y are constructed. To a first approximation, one m a y say t h a t the AO levels are split into bonding and antibomling (and possibly non-bonding) levels. Since a bonding is stronger the splitting of the a levels is supposed to be larger and the bonding and antibonding ~z levels should be closer to the zero-level t h a n the corresponding ~ levels.

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