Amsterdam Density Functional program, Software for Chemistry & Materials NV, Vrije Universiteit, Amsterdam, www.scm.com

Aresta

Bartmess

Bento

Bickelhaupt

Blondel

Born

Boughlala

Bradforth

Brauman

Brewer

Burk

Clayden

Cook

Ellis

Ellison

Ervin

Graul

Grimme

Gurvich

Hamlin

Hanstorp

Harich

Hill

Hunter

Kandel

Klamt

Kolboe

Laloo

Laurence

Lessio

Lewis

Lias

Martin

Mayeux

Mordaunt

Moser

Mulder

Mulliken

Murray

Olah

Onsager

Reed

Ruiz

Ruscic

Schofield

Scribner

Shiell

Smith

Stoyanov

Swart

Szulejko

Terentis

Tsang

Uggerud

Wade

Wickham-Jones

Wolters

Wong

Zaccaria

Zhekova

Ziegler

Boughlala, Zakaria

Fonseca Guerra, Célia

Bickelhaupt, F.M.

Radboud Repository

Chapter four - Cation affinities throughout the periodic table

 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. </p

Bickelhaupt, F. Matthias

VU Research Portal

English

Cation affinities throughout the periodic table

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Chapter Four - Cation affinities throughout the periodic table

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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

van Eldik, Rudi

Puchta, Ralph

Cation affinities throughout the periodic table

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