Colossal Stability of Gas‐Phase Trianions: Super‐Pnictogens

Abstract

Multiply charged negative ions are ubiquitous in nature.T hey are stable as crystals because of charge compensating cations;w hile in solutions,s olvent molecules protect them. However,they are rarely stable in the gas phase because of strong electrostatic repulsion between the extra electrons. Therefore,u nderstanding their stability without the influence of the environment has been of great interest to scientists for decades.While muchofthe past work has focused on dianions, work on triply charged negative ions is sparse and the search for the smallest trianion that is stable against spontaneous electron emission or fragmentation continues.S tability of BeB 11 (X) 12 3À (X = CN,SCN,BO) trianions is demonstrated in the gas phase,w ith BeB 11 (CN) 12 3À exhibiting colossal stability against electron emission by 2.65 eV and against its neutral adduct by 15.85 eV.T he unusual stability of these trianions opens the door to an ew class of super-pnictogens with potential applications in aluminum-ion batteries.

Super-electrophiles of tri- and tetra-anions stabilized by selected terminal groups and their role in binding noble gas atoms

“…25 The exchange-correlation energy functional and basis sets used in this paper have been proven to be capable of providing reliable results in previous works. 6,10,11 Moreover, some theoretical results have been validated by experimental study. 9,13,14 Dispersive interactions are considered in all calculations using the D3 version of Grimme's dispersion with the original D3 damping function.…”

“…The extraordinary stability of B 12 (CN) 12 2À has been recently experimentally confirmed by Mayer et al 9 and the measured second electron affinity of 5.5 eV is in good agreement with the calculated value. Zhao et al 10 then showed that stable gas-phase tri-anions can be formed by tailoring the composition of the boron core of the dianion. They predicted a stable gas-phase tri-anion, BeB 11 (CN) 12 3À , whose third electron is bound by an extraordinarily large value of 2.65 eV.…”