Alkali Metal Cation Affinities of Neutral Maingroup-Element Hydrides across the Periodic Table

We have carried out an extensive quantum chemical exploration of gas-phase alkali metal cation affinities (AMCAs) of archetypal neutral bases across the periodic system using relativistic density functional theory. One objective of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all neutral maingroup-element hydrides XH n of groups 15-18 along the periods 1-6. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a canonical energy decomposition analysis (EDA). We compare the trends in XH n AMCAs with the trends in XH n proton affinities (PAs). We also examine the differences between the trends in AMCAs of the neutral XH n bases with those in the corresponding anionic XH n -1 - bases. Furthermore, we analyze how the cation affinity of our neutral Lewis bases changes along the group-1 cations H + , Li + , Na + , K + , Rb + , and Cs + .