Solvation effects on the molecular 3s Rydberg state: AZAB/CYCLO octanes clustered with argon

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Abstract
Two color, 1+1, mass resolved excitation spectroscopy (MRES) is used to obtain molecular Rydberg (3s←n) spectra of azabicyclo[2.2.2]octane (ABCO) and diazabicyclo[2.2.2]octane (DABCO) clustered with argon. Nozzle/laser timing delay studies are employed together with time‐of‐flight mass spectroscopy to identify cluster composition. Population depletion techniques are used to differentiate between clusters with the same mass, but different geometries. A Lennard‐Jones 6–12 potential is used to model the intermolecular interactions and predict minimum energy cluster geometries and cluster binding energies. The experimental results are combined with the cluster geometry calculations to assign spectral features to specific cluster geometries. Three different excited state interactions are required to model the experimentally observed line shapes, spectral shifts, and cluster dissociation. The relationship between these model potentials and the cluster binding sites suggests that the form of the cluster intermolecular potential in the Rydberg excited state is dictated by the distance between the argon and chromophore atoms. A comparison of results for ABCO(Ar)1 and DABCO(Ar)1 leads to the conclusion that the nitrogen 3s Rydberg orbital in clusters of DABCO is delocalized.

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