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Extra resources for Advances in Chemical Physics: Structure & Properties of Biomolecules, Volume 7
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There are, moreover, three NBMO’s doubly occupied, corresponding to the aza-nitrogens. ABMO NBMO €4 c3 cr BMO ct Fig. 2. Purine: Transitions and energies of the T orbitals (not to scale). 34W These failings are undoubtedly due to the neglect of interelectronic repulsion. (2) Mulliken- Wheland Method This method appears to have been introduced by Mulliken, Rieke, and Brown,82 but was developed extensively by Whelandl24 (which explains its name). This method differs from the Huckel one PT. IA] ELECTRONIC STRUCTURES 29 only in that the overlap between neighbors is not zero, but equal to a constant.
I A ] ELECTRONIC STRUCTURES 21 rotation of the CH2 groups is due to the necessity of breaking the n bond, which requires considerable energy. Recently, Pauling*gv90hasformulated a description of the double bond using Bayer-type hybrids. According to him, the double bond would be formed by two tetrahedral bent bonds from each carbon. G. Localized and Delocalized Bonds When molecules react, the bonds are formed and are broken independently of each other. Because of this, the chemical bond is a “reality” to the classical chemist, with its experimental expression in the constancy of a series of properties, the most important of which are bond length, bond energy, characteristic infrared frequency, dipole moment, quadrupole coupling constant, and chemical “reactivity”.
Likewise Ruedenberg 109 defines a one-electron orbital energy or energy contribution to the total energy, ej, which corresponds to the short-range forces and is obtained as an eigenvalue of a topological one-electron problem. These are additive, and correspond to expression (35), defined as orbital energy. On the other hand, Ruedenberg uses this term for the energy of an electron which occupies an orbital, ej (in particular in SCF orbitals). He also 30 J. I. FERNANDEZ-ALONSO [CHAP. 1 deduces that when the orbital energy contribution, e,, is negative, we have a BMO, and if positive an ABMO, which is consistent with the previous theory.