Geometric isomerism in clusters: High resolution infrared spectroscopy of a noncyclic CO2 trimer

High resolution infrared spectra of a previously unidentified noncyclic isomer of (CO2)(3) have been obtained via direct absorption of a 4.3 mu m diode laser in a slit jet supersonic expansion. Two vibrational bands (labeled nu(I) and nu(III)) are observed, corresponding to the two most infrared active linear combinations of the three constituent CO2 monomer asymmetric stretches: nu(I) is redshifted -5.85 cm(-1) from the monomer vibrational origin and is predominately a c-type band of an. asymmetric top, while nu(III) is blueshifted +3.58 cm(-1) and is predominately an a-type band. Transitions with K-a + K-c = odd (even) in the ground (excited) state are explicitly absent from the spectra due to the zero nuclear spin of CO2; this rigorously establishes that the noncyclic isomer has a C-2 symmetry axis. The vibrational shifts and relative intensities of the bands are interpreted via a resonant dipole interaction model between the high-frequency stretches of the CO2 monomers. Rotational constants are determined by fits of transition frequencies to an asymmetric top Hamiltonian. These results are used to determine vibrationally averaged structural parameters for the complex, which is found to be stacked asymmetric but with C-2 symmetry about the b inertial axis. The structural parameters are then used to test several trial CO2-CO2 interaction potentials. (C) 1996 American Institute of Physics.