Characterization of transition metal–rare-gas cations: VAr+ and VKr+

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Abstract
Resonant photodissociation of supersonically cooled and isolated VKr+ reveals a vibronic progression of a single electronic transition in the visible spectrum. Vibrational analysis of these data indicates an upper state vibrational frequency of 99 cm−1 and a diabatic upper state binding energy of 0.26 eV. Assignment of the dissociation limit of this upper state at 17 419 cm−1 to V+(3d84s 5P2)+Kr(1S0) places the adiabatic binding energy of the ground state of VKr+ at 0.49 eV. The spectrum of VAr+ is analogous to that of VKr+ but shows a somewhat reduced ground state adiabatic binding energy for this molecule, 0.38 eV. A simple inductive binding model is proposed to predict the geometries of these species and parametrize the metal–rare‐gas interatomic potential. This potential is used to gain insight into the factors contributing to the enhanced stability of the ‘‘coordinatively saturated’’ complexes, VAr+4 and CoAr+6.