By W. Kutzelnigg, G. Del Re, G. Berthier
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Extra info for σ and π Electrons in Organic Compounds
Fig. 2 f a n d g Spatial Distributions Fig. 2h. Orbital lblu (~) and that the probability of finding a ~ electron in the molecular plane vanishes. On the other hand, the a electron density has its maximum in the molecular plane. The situation is best illustrated by the orbital density maps of Fig. 2. If the ~ electrons were strictly outside the ~ electron cloud, the potential created by the ~ charge distribution at the position of the ~ electrons would practically vanish, at least in non-polar molecules.
13) is somewhat reduced b y using for the atomic orbital 2p~ of carbon more elaborate forms than a simple Slater function, for instance Hartree-Fock orbitals ~4~. Table 4 gives some values obtained in this way 5~). 33 for two Hartree-Fock functions a~). This shows the im~t ~ 35 The a--~r Separation and the Role of Electron Correlation References see p. 37 portance of an appropriate choice for the basis set of atomic orbitals used in ~ calculations, especially for electronic transitions which depend on the difference between repulsion integrals rather than their absolute values 57).
Chem. Phys. 17, 1248 (1949). ~7) Lykos, P. : J. Chem. Phys. 35, 1249 (1961). 5s) Ellisoa, P. : J. Chcm. Phys. 37, 1414 (1962). ~9) Elliso•, F. , Huff, N. : J. Chem. Phys. 38, 2444 (1963). s0) Orloff, M. : J. Che~n. Phys. ,~3, 49 (1965). 61) Silverstone, It. , Joy, H. : J. Chem. Phys. 47, 1384 (1967). 38 Some C u r r e n t S t a t e m e n t s Concerning a alxd ~ E l e c t r o n s 4. 1. Some Current Statements Concerning a and n Electrons In Chapt. 9. we have recalled how a and ~ orbitals can be defined in terms of a rigorous t h e o r y and w h a t the notions of a and ~ e l e c t r o n s actually mean.