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

✍ Scribed by Marcel Swart; Ernst Rösler; F. Matthias Bickelhaupt

• Book ID: 102305790
• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 233 KB
• Volume: 27
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.20431

✦ Synopsis

Abstract

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. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1486–1493, 2006