Instability of the Al4(2-) "all-metal aromatic" ion and its implications.
Al42 - is a prototype structural unit of a new class of "all-metal aromatic" molecules. Without stabilizing counterions this species is unstable with respect to electron autodetachment in the gas phase. We estimated the height of the repulsive Coulomb barrier to approximately 2.7 eV and calculated a lifetime of 9 fs. This is a short lifetime: The only way to study the isolated dianion experimentally is to use electron scattering techniques. Investigations of the validity of bound-state quantum chemical calculations on the isolated species show that the results suffer from significant admixture of continuum states to the bound-state wave function depending on the basis set. Calculations of molecular properties can therefore give essentially arbitrary results for this ill-defined system, as is demonstrated for the energy and nuclear magnetic shieldings. This substantiates that results from calculations on the isolated dianion should be approached with caution.
Lambrecht
Daniel S
DS
Institut für Theoretische und Computerchemie, Heinrich-Heine-Universität Düsseldorf, Universitätsstr. 1, 40225 Düsseldorf, Germany.
Fleig
Timo
T
Sommerfeld
Thomas
T