STRUCTURE, DYNAMICS, AND SPECTROSCOPY OF ANILINE-(ARGON)(N) CLUSTERS .1. EXPERIMENTAL SPECTRA AND INTERPRETATION FOR N=1-6

An experimental spectroscopic study of the van der Waals aniline-Ar-n, clusters (n = 1-6) has been achieved via resonant two-photon two-colo r ionization, whose results improve the accuracy of the previously rep orted spectra and complete them by the observation of further structur e in the spectra of well-defined structural isomers. These experimenta l results have been analyzed in detail in relation with molecular dyna mics simulations including minimum energy structures calculations, dir ect spectral simulations, and isomerization dynamics. Two potential en ergy surfaces, in both the ground S-0 and the electronically excited S I states, have been built in order to recover the main experimental ob servables. They permit the site specific electronic shift additivity r ule to be confirmed by the semiclassical spectral simulations and a gl obal picture of the solvation phenomena in this aromatic-rare gas atom system to be provided, In particular, careful examination of the isom erization dynamics helps the general understanding of the structural b ehavior of these microsolvent clusters.