Formation of Enormously Strongly Bound Anionic Clusters Predicted in Binary Superacids

Abstract

The possible formation of the (AlF 4 (HF) n ) − (n = 1−8 and 12), (AsF 6 (HF) n ) − , and (SbF 6 (HF) n ) − (n = 1−6 and 12) anionic clusters of a superhalogen nature is predicted in the solutions of binary HF/AlF 3 , HF/AsF 5 , and HF/SbF 5 Lewis−Brønsted superacids on the basis of ab initio calculations. Our results show that all systems investigated represent extremely strongly bound anions characterized by vertical electron detachment energies (VDEs) that significantly exceed 10 eV. The VDE values estimated for the (AlF 4 (HF) 12 ) − , (AsF 6 (HF) 12 ) − , and (SbF 6 (HF) 12 ) − systems are predicted to be 13.96, 14.03, and 14.03 eV, respectively, and are the largest vertical electron detachment energies reported in the literature thus far.

Small lithium‐chloride clusters: Superalkalis, superhalogens, supersalts and nanocrystals

“…The same authors proposed 36 that the species of the types M n X nk +2 , M n X nk +3 , and so forth, where , is the maximal formal valency of M, and X is a monovalent electronegative ligand, could have positive and high values of second and higher EAs. Recently, the molecules with extremely high EAs, as high as 14 eV, were theoretically predicted 37 . The smallest known clusters with positive second EAs have been theoretically predicted to be alkaline trihalides of type MX 3 (M = Li, Na, or K; X = F or Cl) 38 .…”

Electron Propagator Theory of Vertical Electron Detachment Energies of Anions: Benchmarks and Applications to Nucleotides

“…The importance of electron correlation in determining reliable electron detachment energies of superhalide anions was emphasized at an early stage . Metal (M with m valence electrons) halide (X) anions with the general formula M i X mi +1 – that exhibit delocalization of Dyson orbitals over many halogen centers have been especially frequent objects of study. − Extensions to alternative electronegative ligands have been shown to be feasible. − Even organic ligands such as carboxylates and amino acids or fluoroborate tripods were discovered to be suitable for constructing superhalogens. − Connections between the search for more powerful superhalogens with record-setting electron detachment energies and the optimization of superacids with superlative Brønsted acidity have been identified after analysis of electron propagator calculations on icosahedral carboranes. , OF 3 – turns out to be a superhalogen, as do large H n F n +1 – clusters with extraordinarily large electron detachment energies, alkali-metal complexes with borane, HF–MF n – clusters, boron–nitrogen fluoride oligomers, NaCl clusters, noble-gas fluorides, BO 2 – , and (by a narrow margin) BS 2 – . Direct calculation of improvements to canonical Hartree–Fock energies has proven to be a crucial advantage in superhalide clusters where the qualifying electron detachment energy does not correspond to the highest occupied molecular orbital. − For example, in clusters with CN ligands, the order of σ and π orbitals may be reversed by electron correlation.…”

Predicting novel strong acids of plumbylene at theoretical levels

“…[ 19 ] Various Lewis‐Brønsted superacids have been reported at theoretical levels. [ 20–27 ] Strength of Lewis‐Brønsted superacids containing In, Sn, and Sb has been investigated, which employs the B3LYP, QCISD, and OVGF methods. [ 28 ] A new series of superacids was achieved by protonation of B n H 3 n +1 − superhalogen anions, using an MP2/6‐311++G(d,p) basis set.…”