Prediction of many-electron wavefunctions using atomic potentials

For a given many-electron molecule, it is possible to define a corresponding one-electron Schrödinger equation, using potentials derived from simple atomic densities, whose solution predicts fairly accurate molecular orbitals for single- and multi-determinant wavefunctions for the molecule. The ener...

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Bibliographic Details
Published in:The Journal of chemical physics 2017-05, Vol.146 (19), p.194109-194109
Main Authors: Nazari, Fariba, Whitten, Jerry L.
Format: Article
Language:English
Subjects:
Chemical bonds
Configuration interaction
Electrons
Molecular orbitals
Predictions
Schrodinger equation
Wave functions
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Summary:For a given many-electron molecule, it is possible to define a corresponding one-electron Schrödinger equation, using potentials derived from simple atomic densities, whose solution predicts fairly accurate molecular orbitals for single- and multi-determinant wavefunctions for the molecule. The energy is not predicted and must be evaluated by calculating Coulomb and exchange interactions over the predicted orbitals. Potentials are found by minimizing the energy of predicted wavefunctions. There exist slightly less accurate average potentials for first-row atoms that can be used without modification in different molecules. For a test set of molecules representing different bonding environments, these average potentials give wavefunctions with energies that deviate from exact self-consistent field or configuration interaction energies by less than 0.08 eV and 0.03 eV per bond or valence electron pair, respectively.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4983395