%0 Journal Article %1 VONSZENTPALY201672 %A von Szentpály, László %D 2016 %J Computational and Theoretical Chemistry %K Group electronegativity, laszlos Electronegativity Wigner–Witmer theoretische stuttgart affinity, szentpaly DFT chemie symmetry from:alexanderdenzel Valence-pair principles equalization, Conceptual theochem rules, %P 72 - 74 %R https://doi.org/10.1016/j.comptc.2016.02.008 %T Comment on “A new equation based on ionization energies and electron affinities of atoms for calculating of group electronegativity” by S. Kaya and C. Kaya Comput. Theoret. Chem. 1052 (2015) 42–46 %U http://www.sciencedirect.com/science/article/pii/S2210271X16300305 %V 1083 %X Kaya and Kaya’s equation for calculating group electronegativity by global equalization of atomic electronegativities is neither new, nor reliable. Critical comments are presented concerning: (i) the dramatic failure of global ground-state electronegativity equalization (ENE) and the reasons thereof, (ii) the importance of the Wigner–Witmer symmetry laws to obtain accurate ENE in localized bonds, (iii) the electron self-interaction error causing unreasonably small partial charges, (iv) the fact that the “new equation” and global ENE generally yield identical partial charges on all atoms-in-the-molecule of the same element independent of their neighbors, (v) the electron donating power of alkyl groups. Tools and models to correct for the failures and improve the accuracy of local ENE and the resulting partial atomic charges are indicated.

@article{VONSZENTPALY201672, abstract = {Kaya and Kaya’s equation for calculating group electronegativity by global equalization of atomic electronegativities is neither new, nor reliable. Critical comments are presented concerning: (i) the dramatic failure of global ground-state electronegativity equalization (ENE) and the reasons thereof, (ii) the importance of the Wigner–Witmer symmetry laws to obtain accurate ENE in localized bonds, (iii) the electron self-interaction error causing unreasonably small partial charges, (iv) the fact that the “new equation” and global ENE generally yield identical partial charges on all atoms-in-the-molecule of the same element independent of their neighbors, (v) the electron donating power of alkyl groups. Tools and models to correct for the failures and improve the accuracy of local ENE and the resulting partial atomic charges are indicated.}, added-at = {2019-02-08T15:19:18.000+0100}, author = {von Szentpály, László}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2421a839d8db7e8965e9fa5d21c18322b/theochem}, doi = {https://doi.org/10.1016/j.comptc.2016.02.008}, interhash = {18e63cd8baf8b37e56e8cef2c7fc2331}, intrahash = {421a839d8db7e8965e9fa5d21c18322b}, issn = {2210-271X}, journal = {Computational and Theoretical Chemistry}, keywords = {Group electronegativity, laszlos Electronegativity Wigner–Witmer theoretische stuttgart affinity, szentpaly DFT chemie symmetry from:alexanderdenzel Valence-pair principles equalization, Conceptual theochem rules,}, pages = {72 - 74}, timestamp = {2019-02-08T14:19:18.000+0100}, title = {Comment on “A new equation based on ionization energies and electron affinities of atoms for calculating of group electronegativity” by S. Kaya and C. Kaya [Comput. Theoret. Chem. 1052 (2015) 42–46]}, url = {http://www.sciencedirect.com/science/article/pii/S2210271X16300305}, volume = 1083, year = 2016 }