The 1,4-diazabicyclo[2.2.2]octane-Ar-n (n = 1,2,3) van der Waals complexes (DABCO-Ar-n) have been investigated using a combination of (1 + 1') resonance enhanced multiphoton ionization (REMPI) and zero electron kinetic energy (ZEKE) spectroscopy. The additivity of the spectral shifts observed in both REMPI and ZEKE spectra, taken together with analysis of vibrational structure, suggest that in both DABCO-Ar and DABCO-Ar-2 the argon atoms bind in equivalent equatorial (face) locations between two adjacent (CH2)(2) bridges. However, the cumulative evidence from both REMPI and ZEKE spectra, together with ab initio results, suggests that the DABCO-Ar-3 complex does not revert to D-3h symmetry, but rather adopts a C-2v structure in which all three argon atoms bind to one side of the DABCO framework. The exceptionally low wave-number vibrational structure observed in the REMPI spectra suggest that the van der Waals interaction in the excited state is extremely weak. However, ionization necessarily increases the strength of the interaction by virtue of the introduction of charge-induced dipole forces, as revealed by a consistent increase in vibrational wave numbers of the modes observed in the resultant ZEKE spectra. (C) 2004 American Institute of Physics.