Cation affinities throughout the periodic table

Research output: Chapter in Book / Report / Conference proceedingChapterAcademicpeer-review

Abstract

We discuss the concept of cation affinities (CA) and provide an overview of topical trends throughout the periodic table, inferred from state-of-the-art relativistic quantum-chemical computations. The CA of a base B (−) for a cation Y + is the energy or enthalpy required to dissociate the complex BY (+) into molecular fragments B (−) and Y + . Probably the best-known CA is the proton affinity (PA) of Lewis bases. We extend this concept here to include methyl cation (MCA) and other alkyl cation affinities (ACA) as well as alkali metal cation affinities (AMCA). The Lewis bases covered herein are the anionic and neutral element hydrides B = XH n−1 and B = XH n , respectively, as well as methyl-substituted variants thereof. The element “X” in our model Lewis bases covers the maingroup elements of groups 14–18 in rows 1–6 of the periodic table. Emerging trends are analyzed and explained in terms of quantitative molecular orbital (MO) theory as contained in Kohn–Sham density functional theory (KS-DFT). Making the often implicitly used idea of a CA explicit serves a more rational design of compounds with a particular affinity for, or reactivity toward, other species throughout the molecular sciences, from inorganic via organic to biological chemistry.

Original languageEnglish
Title of host publicationComputational Chemistry
EditorsRudi van Eldik, Ralph Puchta
PublisherAcademic Press Inc.
Chapter4
Pages123-158
Number of pages36
ISBN (Electronic)9780128157299
ISBN (Print)9780128157282
DOIs
Publication statusPublished - 2019

Publication series

NameAdvances in Inorganic Chemistry
Volume73
ISSN (Print)0898-8838

Fingerprint

Cations
Lewis Bases
Alkali Metals
Molecular orbitals
Hydrides
Density functional theory
Protons
Enthalpy

Keywords

  • Bond theory
  • Cation affinities
  • Density functional calculations
  • Proton affinities
  • Thermochemistry

Cite this

Boughlala, Z., Fonseca Guerra, C., & Bickelhaupt, F. M. (2019). Cation affinities throughout the periodic table. In R. van Eldik, & R. Puchta (Eds.), Computational Chemistry (pp. 123-158). (Advances in Inorganic Chemistry; Vol. 73). Academic Press Inc.. https://doi.org/10.1016/bs.adioch.2018.10.004
Boughlala, Zakaria ; Fonseca Guerra, Célia ; Bickelhaupt, F. Matthias. / Cation affinities throughout the periodic table. Computational Chemistry. editor / Rudi van Eldik ; Ralph Puchta. Academic Press Inc., 2019. pp. 123-158 (Advances in Inorganic Chemistry).
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Boughlala, Z, Fonseca Guerra, C & Bickelhaupt, FM 2019, Cation affinities throughout the periodic table. in R van Eldik & R Puchta (eds), Computational Chemistry. Advances in Inorganic Chemistry, vol. 73, Academic Press Inc., pp. 123-158. https://doi.org/10.1016/bs.adioch.2018.10.004

Cation affinities throughout the periodic table. / Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F. Matthias.

Computational Chemistry. ed. / Rudi van Eldik; Ralph Puchta. Academic Press Inc., 2019. p. 123-158 (Advances in Inorganic Chemistry; Vol. 73).

Research output: Chapter in Book / Report / Conference proceedingChapterAcademicpeer-review

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Boughlala Z, Fonseca Guerra C, Bickelhaupt FM. Cation affinities throughout the periodic table. In van Eldik R, Puchta R, editors, Computational Chemistry. Academic Press Inc. 2019. p. 123-158. (Advances in Inorganic Chemistry). https://doi.org/10.1016/bs.adioch.2018.10.004