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The three‐center bond model for molecular electronic structure
Author(s) -
Cullen John M.,
Lipscomb William N.,
Zerner Michael C.
Publication year - 1984
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560260840
Subject(s) - antibonding molecular orbital , delocalized electron , center (category theory) , atomic orbital , bond order , perturbation theory (quantum mechanics) , molecular orbital , chemistry , molecular physics , computational chemistry , physics , quantum mechanics , bond length , molecule , crystallography , electron
The Rayleigh–Schrödinger perturbation theory for a localized nonorthogonal basis of three‐center bonding and antibonding orbitals is examined up to fourth order. Results are reported utilizing the Hückel and Pariser–Parr–Pople model Hamiltonians and compared with those determined from the two‐center bonding model and with exact results when they are known. The three‐center bond model is found to be especially useful in the treatment of delocalized systems in which the slow convergence of the two‐center bonding schemes leads to ambiguities in the relative energies of identical conformations as well as incorrect geometry predictions.