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: Medrano, J.A., Bochicchio, R.C.
Formato: JOUR
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_01661280_v200_nC_p463_Medrano
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spelling todo:paper_01661280_v200_nC_p463_Medrano2023-10-03T15:03:12Z The UHF extension of the quantum theory of valence and bonding Medrano, J.A. Bochicchio, R.C. 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. Fil:Medrano, J.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Bochicchio, R.C. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_01661280_v200_nC_p463_Medrano
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description 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.
format JOUR
author Medrano, J.A.
Bochicchio, R.C.
spellingShingle Medrano, J.A.
Bochicchio, R.C.
The UHF extension of the quantum theory of valence and bonding
author_facet Medrano, J.A.
Bochicchio, R.C.
author_sort Medrano, J.A.
title The UHF extension of the quantum theory of valence and bonding
title_short The UHF extension of the quantum theory of valence and bonding
title_full The UHF extension of the quantum theory of valence and bonding
title_fullStr The UHF extension of the quantum theory of valence and bonding
title_full_unstemmed The UHF extension of the quantum theory of valence and bonding
title_sort uhf extension of the quantum theory of valence and bonding
url http://hdl.handle.net/20.500.12110/paper_01661280_v200_nC_p463_Medrano
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AT medranoja uhfextensionofthequantumtheoryofvalenceandbonding
AT bochicchiorc uhfextensionofthequantumtheoryofvalenceandbonding
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