Populational Decoupling of Atomic Orbitals

Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek 

This failure to properly reflect the intuitive MO-population trends by the IT bond indices calls for a thorough revision of the hitherto used overall communication channel in AO resolution, which combines the contributions from all occupied MOs in the electron configuration in question. Instead, one could envisage a use of the separate MO channels introduced in Section 2 (Eq. [7b]). As an illustration, let us assume for simplicity the two-AO model of the chemical bond A-B originating from the quantum-mechanical interaction between two AOs x = ( e A, b e B). The bond contributions between this pair of AO in the information system of sth MO, 

Consider now another model system of the n electrons in allyl, with the consecutive numbering of 2pz = z orbitals in the carbon chain. In the Hiickel approximation, it is described by two occupied (canonical) MOs  

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IT bond increments for each occupied MO. We shall implement this idea in Section 5, when tackling the populational decoupling of atomic orbitals, as a result of an increased occupation of the antibonding MO. 

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