Solvent shifts in van der waals complexes of perylene

Abstract The solvation and structure of vdW complexes formed in supersonic free-jet expansions of perylene with rare gas atoms and organic “solvent” molecules, using helium as carrier gas, have been investigated. The complexes were probed and analysed by combining laser-induced fluorescence spectroscopy with approximate summed pair-potential calculations. Theoretical examination of the bathochromic spectral shifts for the isolated 1:1 vdW complexes is consistent between solvent-shift theory and equilibrium configuration calculations. Analysis of the spectral shifts assumes they arise solely through the change in dispersion energies on electronic excitation and that this difference can be estimated using average excitation energies.