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Thermal dissociation of 1,2‐dioxethane. III. Localized molecular‐orbital study
Author(s) -
Hilal Rifaat
Publication year - 1981
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.560190513
Subject(s) - dissociation (chemistry) , dipole , saddle point , chemistry , atomic physics , lone pair , charge density , potential energy surface , potential energy , electron , chemical physics , molecular physics , physics , molecule , quantum mechanics , geometry , mathematics , organic chemistry
Abstract The localized MO 's ( LMO 's) of 1,2‐dioxethane in its ground state and along the dissociation reaction path (to formaldehyde products) are generated using Boys' criteria for localization. The total charge density in each LMO is partitioned into atomic and overlap densities and the binding or antibinding character of each LMO is discussed in terms of the forces exerted on the nuclei by these densities. The driving force for the dissociation reaction is shown to arise essentially from the atomic dipole forces exerted on the oxygen nuclei by their lone‐pair LMO 's. The characterization of a saddle point on the potential energy surface has been discussed in terms of the electrostatic equilibrium between forces exerted by the electron clouds “incomplete following” and “preceding.” The differences between the LMO 's obtained from the two Hartree–Fock solutions to which the SCF procedure converges have been discussed.