Infrared spectra of both isomers of CO$_2$-CO in the CO$_2$ $\nu_3$ region

Abstract

Extensive infrared spectra of the weakly-bound CO$_2$-CO dimer are observed in the carbon dioxide $\nu_3$ asymmetric stretch region (~2350 cm-1) using a tunable infrared OPO laser source to probe a pulsed slit jet supersonic expansion. Both C-bonded and O-bonded isomers are analyzed for the normal isotopologue as well as for 13CO$_2$-CO and $^{16}$O$^{13}$C$^{18}$O-CO, the latter being the first observation of an asymmetrically substituted form for which all values of Ka are allowed. Combination bands involving the lowest in-plane intermolecular bending modes are also studied for both isomers. Weak bands near 2337 cm-1 are assigned to CO$_2$ hot band transitions (v1, v2l2, v3) = (0111) <-- (0110), yielding the splitting of the degenerate CO$_2$ $\nu_2$ bend into in-plane and out-of-plane components due to the presence of the CO. This splitting has rather different values for the C- and O- bonded isomers, 4.56 and 1.59 cm-1, respectively, with the out-of-plane mode higher in energy than the in-plane for both cases.