Transition-metal solvated-electron precursors: diffuse and 3d electrons in V(NH3) 0,±6

Abstract

Ground and excited electronic states of V(NH₃)^0,±₆ complexes, investigated with ab initio electronic structure theory, consist of a V(NH₃)₆²⁺ core with up to three electrons distributed over its periphery. This result extends the concept of super-atomic, solvated-electron precursors from alkali and alkaline-earth complexes to a transition metal. In the approximately octahedral ground state of V(NH₃)₆, three unpaired electrons occupy 3d_xz, 3d_yz and 3d_xy (t_2g) orbitals of vanadium and two electrons occupy a diffuse 1s outer orbital. The lowest excitations involve promotion of diffuse 1s electrons to 1p or 1d diffuse orbitals, followed by a 3d (t_2g → e_g) transition. V(NH₃)₆⁺ is produced by removing a diffuse 1s electron, whereas the additional electron in V(NH₃)₆⁻ populates a 1p diffuse orbital. The adiabatic ionization energy and electron affinity of V(NH₃)₆ equal 3.50 and 0.48 eV, respectively.