Steric Effects on Alkyl Cation Affinities of Maingroup-Element Hydrides

We have carried out an extensive exploration of gas-phase alkyl cation affinities (ACA) of archetypal anionic and neutral bases across the periodic system using zeroth order regular approximation-relativistic density functional theory at BP86/QZ4P//BP86/TZ2P. ACA values were computed for the methyl, ethyl, i-propyl and t-butyl 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 ACA of all anionic (XHân-1-) and neutral bases (X