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

M. Swart, E. Rosler, F.M. Bickelhaupt

Research output: Contribution to JournalArticleAcademicpeer-review

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.
Original languageEnglish
Pages (from-to)1486-93
JournalJournal of Computational Chemistry
Volume27
Issue number13
DOIs
Publication statusPublished - 2006

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