Spectroscopic studies of cryogenic fluids: Benzene in argon and helium

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Energy shifts and bandwidths of the 610 vibronic feature of the 1B2u←1A1g optical absorption spectrum of benzene dissolved in supercritical argon and helium, and in liquid argon are reported as a function of pressure, temperature, and density. Benzene/Ar solutions display red shifts of the 610 transition with increasing density but the dependence is found to be nonlinear at high densities. Benzene/He solutions evidence blue shifts of the 610 transition as a function of increasing density which also becomes nonlinear at high densities. Only small spectral shifts are recorded if the density is kept constant and pressure and temperature are varied simultaneously. In addition, a small density independent temperature effect on the transition energy shift is identified. Experimental results are compared to dielectric (Onsager–Böttcher and Wertheim) and quantum statistical mechanical (Schweizer–Chandler) theories of solvent effects on solute absorption energy. Reasonably good agreement between experiment and theory is found only for the benzene/Ar system at relatively low densities. The theory fails to predict energy shifts for both the benzene/He and high density benzene/Ar systems. This result is different from the findings for the benzene/N2 and benzene/C3H8 solutions and can be interpreted qualitatively in terms of competition between dispersive attractive and repulsive interactions as a function of density. The failure of the theory to describe these transition energy shifts is attributed to the omission of explicit repulsive interactions terms in the theoretical models employed.