(1+1(')) resonance enhanced multiphoton ionization (REMPI) spectra of jet-cooled KrXe and ArXe in the vicinity of the high energy Xe*5d[3/2](1)(0)<-- Xe(S-1(0)) atomic line at 83889.99 cm(-1) were obtained by exciting the neutral dimers with tunable coherent vacuum ultraviolet (VUV) radiation generated by four-wave sum mixing in mercury vapor, and then detecting the resultant ions in a time-of-flight (TOF) mass spectrometer. Precise excited state constants were derived from analyses of the resultant vibrational fine structure, while equilibrium bond lengths were estimated from Franck-Condon factor intensity simulations. Excited state symmetries were deduced from separate ultraviolet (UV) (2+1) REMPI spectra recorded with linearly and circularly polarized light. The results of this work confirm a recent model proposed by Lipson and Field, where the RgXe*(5d) states are predicted to be strongly destabilized relative to RgXe*(6p) due to strong 5d-6p Xe* l-mixing induced by the ground state Rg atom partner making up the dimer. Orbital mixing is also responsible for the observation of appreciably strong RgXe(*)(5d) spectra in both one- and two-photon excitation.