Extracting covalent and ionic structures from usual delocalized wave functions: the electron-expansion methodology

The Journal of Physical Chemistry. a
P Papanikolaou, P Karafiloglou

Abstract

We present easily programmable expansions, allowing the calculation of the weights of local covalent and ionic structures of a chemical bond from usual delocalized wave functions; they are obtained in the framework of the electron-expansion methodology, in which the hole conditions (involved by definition in a covalent or ionic structure) are expanded in terms involving only electrons. From the derived relations, true for both HF and correlated levels, one can also express the covalency/ionicity and the localization of a usual two-electron two-center (2e/2c) bond in terms of electronic populations. The three-electron populations are crucial for bond localization. On the contrary, in 2e/2c bonding, and particularly in Charge-Shift bonds (which show enhanced covalent-ionic interactions) although the three-electron populations can be non-negligible, they are not important for the covalency/ionicity of these bonds. Numerical applications and discussion are given for correlated MO wave functions of butadiene, hexatriene, and pyrrole molecules on the basis of both natural atomic orbitals (NAOs) (orthogonal orbitals) and pre-NAOs (nonorthogonal orbitals).

References

Aug 12, 2000·Chemistry : a European Journal·J M GalbraithP C Hiberty
Oct 11, 2003·The Journal of Organic Chemistry·Robert Ponec, Gleb Yuzhakov
Oct 22, 2005·The Journal of Chemical Physics·Diego R AlcobaRoberto C Bochicchio
Mar 2, 2006·Journal of the American Chemical Society·Philippe C HibertySason Shaik
Jul 13, 2006·The Journal of Physical Chemistry. a·Robert PonecAna Gallegos Saliner
Jul 21, 2006·The Journal of Physical Chemistry. a·Atsushi IkedaShigeyoshi Sakaki
Sep 20, 2006·Journal of Computational Chemistry·Padeleimon Karafiloglou
Oct 27, 2006·Journal of Computational Chemistry·Patrick BultinckRamon Carbó-Dorca
Mar 3, 2007·Faraday Discussions·Philippe C HibertySason Shaik

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Citations

Jan 4, 2017·The Journal of Physical Chemistry. a·Masayoshi NakanoBenoît Champagne
Sep 3, 2019·Angewandte Chemie·Sason ShaikPhilippe C Hiberty
Jul 14, 2009·Journal of Chemical Theory and Computation·Atsushi IkedaShigeyoshi Sakaki

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