van der Waals rovibration levels and the high resolution spectrum of the argon–benzene dimer

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Abstract
The van der Waals vibrations of Ar–benzene are calculated from two different intermolecular potentials, which are analytic fits to the same ab initio potential. The rovibrational Hamiltonian was derived earlier; the wave functions of the large amplitude vibrations are expanded in products of harmonic oscillator functions. The rotational structure of each van der Waals state is obtained from perturbation theory, as well as from variational calculations of the complete rovibrational states for J=0, 1, and 2. The degenerate bending modes and combinations have a large vibrational angular momentum; for their rotational structure it is important to include all first, second, and higher order rovibrational (Coriolis) coupling. The calculated vibrational frequencies, the information about rovibrational coupling, and the PI(C 6v ) selection rules for van der Waals transitions, in combination with the vibronic 60 1 transition on the benzene monomer, lead to a partially new assignment of the three van der Waals sidebands observed in high resolution UV spectra.