Early in their education, students of chemistry learn the importance of electron pairs in understanding chemical bonding. Two, familiar types of electron pairs, those involved in chemical bonding between atoms and those that are confined in a non-bonding fashion to a single atom, are described by interference between valence atomic orbitals. Photoelectron spectra and ab initio calculations have shown that positively charged molecular ions are capable of binding two extra electrons in species known as double Rydberg anions (DRAs). Dyson orbitals of anion photo-detachment reveal that a different kind of electron pair, characterized by diffuse distribution over the periphery of a positive ion and stabilized by electron correlation, occurs in DRAs such as NH4-, OH3- and PH4- and in larger species stabilized by hydrogen bonds or polarizable substituents. Similar anions with diffuse electron pairs also may be synthesized from metallic elements.

Double Rydberg anions and their Dyson orbitals

254th National Meeting (2017)

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