A derivation of the exact pi-electron hamiltonian |
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Authors: | K.F. Freed |
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Affiliation: | The Department of Chemistry and The James Franck Institute, The University of Chicago, Chicago, Illinois 60637, USA |
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Abstract: | The exact pi-electron hamiltonian is derived from the full many-electron Schrödinger equation. The derivation employs techniques which also enable the development of open shell generalized perturbation theory. The parameters occurring in the pi-hamiltonian are therefore amenable to calculation using the approximate theories and methods of Sinano?lu, Nesbet, Kelly, etc. To a good approximation, the pi-hamiltonian is found to be generally consistent with its customarily assumed form. |
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