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Chem Asian J. 2017 Oct 5;12(19):2604-2611. doi: 10.1002/asia.201700956. Epub 2017 Sep 13.

Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table.

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Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, NL.
Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA, Leiden, NL.
Institute of Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ, Nijmegen, NL.


We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XHn-1- ) constituted by main group-element hydrides of groups 14-17 along the periods 2-6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA).


alkali metal cation affinities; bond theory; density functional calculations; proton affinities; thermochemistry


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