Exotic Bonding Regimes Uncovered in Excited States

Abstract

Abstract Real‐space tools were employed to show that the chemical bonding scenario used routinely to understand ground states lacks the necessary flexibility in excited states. It is shown that, even for two‐center, two‐electron bonds, the real‐space bond orders have exotic values that have never been reported. The nature of these situations was uncovered by using electron‐counting techniques that provide an appealing statistical interpretation of bonding descriptors, together with simple physical models. Bond orders greater than one as well as negative bond orders for a single bonding electron pair emerge in situations in which the electrons in the pair show a gregarious (bosonic) instead of the usual lonely (fermionic) behavior. In the first case the gregarious pair is intra‐atomic, whereas the coupling is interatomic in the second. A number of examples are used to substantiate these claims.

Evelio Francisco Miguélez

Associate Professor

Associate Professor of Physical Chemistry at the University of Oviedo. Expert in the development and application of quantum chemical topology methods, IQA analysis, and electron correlation descriptors.