The UHF extension of the quantum theory of valence and bonding
General definitions of the empirical notions of classical chemistry, such as valence and degree of bonding, have been given before. These definitions use the density matrix of the system and can be applied to any type of SCF-LCAO-MO wavefunction, whether ab initio or semiempirical. However, we find...
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| Autores principales: | , |
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| Formato: | JOUR |
| Acceso en línea: | http://hdl.handle.net/20.500.12110/paper_01661280_v200_nC_p463_Medrano |
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| Sumario: | General definitions of the empirical notions of classical chemistry, such as valence and degree of bonding, have been given before. These definitions use the density matrix of the system and can be applied to any type of SCF-LCAO-MO wavefunction, whether ab initio or semiempirical. However, we find in this paper that the discussion that has been provided before for the open-shell unrestricted Hartree-Fock (UHF) case [M.A. Natiello, H.F. Reale and J.A. Medrano, J. Comput. Chem., 6 (1985) 108] is incomplete and faulty. We now give the correct derivation for this important case. We show how this statistical population analysis (SPA) relates to the problem of calculating mean occupation numbers of molecular orbitals, and we also give definitions for other magnitudes related to the charge associated with different regions within the molecule. Finally we report the result of application to some selected molecules. © 1989. |
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