Theoretical Search for Anions Possessing Large Electron Binding Energies

Abstract

AbstractThe vertical electron detachment energies (VDE) of several anions were calculated at the OVGF level with 6‐311++G(d) basis sets. The negatively charged species studied were chosen based on the observation that the largest electron binding energies for such systems are expected to be found for the anions whose neutral parents are polynuclear superhalogens. The largest vertical electron binding energy of 12.63 eV was found for Ta3F16−, and this is the largest excess electron binding energy of a molecular system reported in the literature thus far. Moreover, the VDEs of 12.63 and 12.20 eV calculated for Ta3F16− and As3F16−, respectively, exceed the upper limit for the excess electron binding energy (thought to be 12 eV). Several other anions were also found [at the OVGF/6‐311++G(d) level] to possess very large VDEs (i.e. Al2Br7−: 7.08 eV, Al2Cl7−: 7.75 eV, Al2F7−: 11.16 eV, P2F11−: 10.95 eV, V2F11−: 10.98 eV, As2F11−: 11.43 eV, and Ta2F11−: 11.84 eV). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)