Diffuse electron pairs that surround saturated, closed-shell cations in double Rydberg anions such as tetrahedral NH4- and its NnH3n+1- generalizations or in solvated-electron precursors such as Be(NH3)4 can also occur in high-spin, transition-metal complexes with ammonia ligands such as V(NH3)6. Dative bonds from ammonia lone pairs to cationic cores are strong enough to expel valence s electrons of metal atoms to the periphery of each complex, where they are subject to a non-hydrogenic Aufbau principle that governs ground and excited states. Dyson orbitals calculated with ab initio electron propagator methods confirm the validity of this Aufbau principle when more than two diffuse electrons are present. Two-component, relativistic extensions of electron-propagator methods that describe spin-orbit splittings in terms of complex, non-colinear Dyson orbitals have considerable promise in the discovery of Rydberg anions and solvated electron precursors with 3d, 4d and 5d transition-metal atoms.

Diffuse and magnetic Dyson orbitals in the Rydberg anions and solvated-electron precursors of transition-metal chemistry

2019 Fall National Meeting

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