Fei Wang - Deciphering the Chemical Bonding in Anionic Thallium Clusters

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      Publication Details (including relevant citation   information):

      Fei Wang, Ulrich Wedig, Dasari L. V. Prasad, and Martin Jansen,   J. Am. Chem. Soc., 2012, 134, 19884-19894.


      The chemical bonding schemes of thallium cluster anions commonly   comply with neither Wade–Mingos’s rules nor the Zintl–Klemm   concept and thus far have escaped a fully consistent description.   In general, the number of electrons available for the cluster   skeleton bonding fall below those required according to the   qualitative concepts mentioned and the clusters were labeled   “hypoelectronic”. Based on fully relativistic band structure   calculations on respective complete extended solids and   electronic structure calculations on excised, charge compensated,   and geometrically optimized clusters, we have identified two   mechanisms that are suited to lift the degeneracy of partially   filled electronic states and to open a ****–LUMO gap, the   Jahn–Teller effect and relativistic spin–orbit coupling.   Treatment on this level of theory shows that, in accordance with   experiment, the thallium cluster anions known are electronically   saturated and not deficient in valence electrons. We provide   qualitative group theoretical procedures for analyzing the   Jahn–Teller effect and spin–orbit coupling in lifting the   degeneracy of frontier orbitals in highly symmetric thallium   cluster anions.

      Address (URL): http://pubs.acs.org/doi/abs/10.1021/ja309852f