Proton affinities of maingroup-element hydrides and noble gases : trends across the periodic table, structural effects, and DFT validation
Copyright 2006 Wiley Periodicals, Inc.
Veröffentlicht in: | Journal of computational chemistry. - 1984. - 27(2006), 13 vom: 05. Okt., Seite 1486-93 |
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Weitere Verfasser: | , |
Format: | Aufsatz |
Sprache: | English |
Veröffentlicht: |
2006
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Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
Schlagworte: | Journal Article |
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 |
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Beschreibung: | Date Completed 25.06.2007 Date Revised 30.08.2006 published: Print Citation Status PubMed-not-MEDLINE |
ISSN: | 1096-987X |