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

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

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).

LanguageEnglish
Pages2604-2611
Number of pages8
JournalChemistry - An Asian Journal
Volume12
Issue number19
DOIs
Publication statusPublished - 5 Oct 2017

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Alkali Metals
Hydrides
Cations
Protons
Rubidium
Tranexamic Acid
Cesium
Time varying systems
Alkalies
Molecular orbitals
Lithium
Density functional theory
Potassium
Gases
Sodium
Decomposition

Keywords

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

Cite this

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abstract = "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).",
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Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table. / Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F. Matthias.

In: Chemistry - An Asian Journal, Vol. 12, No. 19, 05.10.2017, p. 2604-2611.

Research output: Contribution to JournalArticleAcademicpeer-review

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