Premium
The correlation of proton affinities with atomic charges and electronegativities for the group 14 to 17 hydrides
Author(s) -
de Souza Hermes F.,
Guadagnini Paulo H.,
Custodio Rogério,
Goddard John D.
Publication year - 2000
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/1096-987x(200010)21:13<1119::aid-jcc1>3.0.co;2-q
Subject(s) - electronegativity , affinities , chemistry , proton affinity , protonation , group (periodic table) , proton , basis set , lone pair , computational chemistry , periodic table , electron affinity (data page) , hydrogen bond , main group element , basis (linear algebra) , electronic correlation , molecule , crystallography , atomic physics , stereochemistry , density functional theory , quantum mechanics , physics , mathematics , geometry , organic chemistry , transition metal , ion , catalysis
Proton affinities for hydrides of formula \documentclass{article}\pagestyle{empty}\begin{document}$\mathrm{AH}^{-}_{n-1}$\end{document} containing the elements A from the second to the fifth period of the periodic table and groups 14 to 17 are predicted at the Hartree–Fock, MP2 and B3LYP levels of theory employing both core potential basis sets and the 3‐21G basis set. The core potential methods perform well when compared with all electron calculations using the 3‐21++G** basis set. The proton affinities of the hydrides containing elements from groups 15 and 16 of the periodic table are more accurate than those with elements from groups 14 and 17. A cancellation of errors appears to occur more completely if the protonated and nonprotonated molecules contain both bond and lone pairs before and after the protonation reaction. Proton affinities correlate nearly linearly with the atomic charges on the hydrogen atoms when these charges are determined by the generalized atomic polar tensor (GAPT) method. This tendency can be associated, in principle, with the group electronegativities as introduced by Iczkowski and Margrave. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1119–1131, 2000