Infrared spectroscopy of Ar2CO2 trimer: Vibrationally averaged structures, solvent shifts, and three-body effects

Abstract

Ar2CO2 is studied using direct absorption infrared spectroscopy. The van der Waals molecules are formed when a mixture of CO2 and Ar gases is expanded in a supersonic slit jet. To probe the clusters, the ν3 asymmetric stretch of the CO2 monomer is then monitored in absorption. Sixty-one trimer transitions are assigned and fit to a Watson asymmetric top Hamiltonian. Rotational constants for the upper and lower vibrational states permit determination of vibrationally averaged molecular structures, which indicate that the Ar atoms lie in the plane that bisects CO2 and is perpendicular to the CO2 intramolecular axis. These geometries are consistent with an equivalent ‘‘T-shaped’’ ArCO2 geometry for each Ar atom. Vibrational origins for the ν3 CO2 asymmetric stretch frequency in ArnCO2 are found to shift approximately linearly for zero, one, and two Ar atoms. Calculations using pair potentials are used to extrapolate these red shifts out to the bulk phase and to compare the results to experimental matrix data. Finally, the slight nonlinearity in the red shift between ArCO2 dimer and Ar2CO2 trimers is interpreted in the context of three-body forces.