Mixed valence/dipole-bound dianions

摘要

The possibility of binding two electrons to a molecule utilizing two distinct electron binding sites (i.e., one valence- and one dipole-binding center) is studied using ab initio electronic structure methods. It is found that if the electron binding energy of the dipole-binding site is large enough to overcome the Coulomb repulsion produced by the valence-bound electron, the dianion can be electronically stable with respect to the corresponding monoanion. It is also found that, for reasonable dipole- and valence-binding strengths, the separation between the two sites can be small enough to render the species within the current realm of synthetic possibility. Numerical results are presented for the dianions of LiCN…LiCC-PF_5 and LiCN…LiCN225L璍iCC-PF_5, whose vertical electronic stabilities are 0.120 and 0.808 eV, and whose stabilities with respect to fragmentation (i.e., loss of LiCN~-) are 3.9 and 36.5 kcal/mol [including zero point energy (ZPE)], respectively.