Proton affinities of maingroup-element hydrides and noble gases : trends across the periodic table, structural effects, and DFT validation

Copyright 2006 Wiley Periodicals, Inc.

Bibliographische Detailangaben
Veröffentlicht in:Journal of computational chemistry. - 1984. - 27(2006), 13 vom: 05. Okt., Seite 1486-93
1. Verfasser: Swart, Marcel (VerfasserIn)
Weitere Verfasser: Rösler, Ernst, Bickelhaupt, F Matthias
Format: Aufsatz
Sprache:English
Veröffentlicht: 2006
Zugriff auf das übergeordnete Werk:Journal of computational chemistry
Schlagworte:Journal Article
Beschreibung
Zusammenfassung:Copyright 2006 Wiley Periodicals, Inc.
We have carried out an extensive exploration of the gas-phase basicity of archetypal neutral bases across the periodic system using the generalized gradient approximation (GGA) of the density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. First, we validate DFT as a reliable tool for computing proton affinities and related thermochemical quantities: BP86/QZ4P//BP86/TZ2P is shown to yield a mean absolute deviation of 2.0 kcal/mol for the proton affinity at 298 K with respect to experiment, and 1.2 kcal/mol with high-level ab initio benchmark data. The main purpose of this work is to provide the proton affinities (and corresponding entropies) at 298 K of the neutral bases constituted by all maingroup-element hydrides of groups 15-17 and the noble gases, that is, group 18, and periods 1-6. We have also studied the effect of step-wise methylation of the protophilic center of the second- and third-period bases
Beschreibung:Date Completed 25.06.2007
Date Revised 30.08.2006
published: Print
Citation Status PubMed-not-MEDLINE
ISSN:1096-987X