Cation affinities throughout the periodic table

Zakaria Boughlala, Célia Fonseca Guerra, F. Matthias Bickelhaupt*

*Corresponding author for this work

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


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.
Number of pages36
ISBN (Electronic)9780128157299
ISBN (Print)9780128157282
Publication statusPublished - 2019

Publication series

NameAdvances in Inorganic Chemistry
ISSN (Print)0898-8838


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


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