Hydride affinities of cationic maingroup-element hydrides across the periodic table

Abstract

We have quantum chemically explored the gas-phase hydride affinities (HA) of archetypical cationic Lewis acids across the periodic table, using relativistic density functional theory (DFT) at ZORA-BP86/QZ4P. One purpose of this work is to establish an intrinsically consistent set of values of the 298 K HAs of all cationic maingroup-element hydrides (XHn–1+) in which we have varied the central atom X along groups 14–17 and periods 2–6. Our main purpose is to understand the emerging trends in HA values in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital (MO) theory together with a quantitative bond energy decomposition analysis (EDA).