Exploring the anharmonic vibrational structure of carbon dioxide trimers.

Our previously developed mbCO2 potential [O. Sode and J. N. Cherry, J. Comput. Chem. 38, 2763 (2017)] is used to describe the vibrational structure of the intermolecular motions of the CO2 trimers: barrel-shaped and cyclic trimers. Anharmonic corrections are accounted for using the vibrational self-consistent field theory, vibrational second-order Møller-Plesset perturbation (VMP2) theory, and vibrational configuration interaction (VCI) methods and compared with experimental observations. For the cyclic structure, we revise the assignments of two previously observed experimental peaks based on our VCI and VMP2 results. We note that the experimental band observed near 13 cm-1 is the out-of-phase out-of-plane degenerate motion with E″ symmetry, while the peak observed at 18 cm-1 likely corresponds to the symmetric out-of-plane torsion A″ vibration. Since the VCI treatment of the vibrational motions accounts for vibrational mixing and delocalization, overtones and combination bands were also observed and quantified in the intermolecular regions of the two trimer isomers.