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Proton affinities of maingroup‐element hydrides and noble gases: Trends across the periodic table, structural effects, and DFT validation
Author(s) -
Swart Marcel,
Rösler Ernst,
Bickelhaupt F. Matthias
Publication year - 2006
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/jcc.20431
Subject(s) - affinities , chemistry , density functional theory , proton , computational chemistry , proton affinity , ab initio , yield (engineering) , periodic table , gas phase , thermodynamics , stereochemistry , organic chemistry , nuclear physics , physics , ion , protonation
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