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Exotic bonding regimes uncovered in excited states.

Real space tools are employed to show that the chemical bonding scenario used routinely to understand ground states lacks the necessary flexibility in excited states. We show that even for two-center, two-electron links the real space bond orders admit exotic values that have never been reported. The nature of these situations is uncovered by using electron counting techniques that provide an appealing statistical interpretation of bonding descriptors, together with simple physical models. Greater than one as well as negative bond orders for a single bonding electron pair are shown to emerge in situations where 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, while the coupling is interatomic in the second. A number of examples are used to substantiate our claims.