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Only a few weakly-bound complexes containing the O2 molecule have beencharacterized by high resolution spectroscopy, no doubt due to thecomplications added by the oxygen molecule's unpaired electron spin. Here wereport an extensive infrared spectrum of CO-O2, observed in the CO fundamentalband region using a tunable quantum cascade laser to probe a pulsed supersonicjet expansion. The rotational energy level pattern derived from the spectrumconsists of stacks of levels characterized by the total angular momentum, J,and its projection on the intermolecular axis, K. Five such stacks are observedin the ground vibrational state, and ten in the excited state (v(CO) = 1). Theyare divided into two groups, with no observed transitions between groups. Thegroups correspond to different projections of the O2 electron spin, andcorrelate with the two lowest rotational states of O2, (N, J) = (1, 0) and (1,2). The rotational constant of the lowest K = 0 stack implies an effectiveintermolecular separation of 3.82 Angstroms, but this should be interpretedwith caution since it ignores possible effects of electron spin. A newhigh-level 4-dimensional potential energy surface is developed for CO-O2, androtational energy levels are calculated for this surface, ignoring electronspin. By comparing calculated and observed levels, it is possible to assigndetailed quantum labels to the observed level stacks.

Infrared spectrum and intermolecular potential energy surface of the CO-O2 dimer