A broad-band (2135-2200 cm(-1)) infrared spectrum of the CO dimer is recorded using a tunable quantum cascade laser to probe a supersonic jet expansion with an effective rotational temperature of about 2.5 K. Analysis of the spectrum reveals the first known levels of the excited state (vCO = 1) with A(+) symmetry and establishes that resonant vibrational splittings are small (<0.2 cm(-1)) for both the C-bonded and O-bonded dimer isomers. The spectrum extends over a surprisingly large range, with somewhat reduced intensity above 2150 cm(-1). A total of 28 new "stacks" of rotational levels having A(-) symmetry are assigned for vCO = 1 on the basis of combination differences, adding to the 8 stacks previously known, and extending up to 51 cm(-1) above the vCO = 1 origin. Assignments are given for the first 13 stacks of vCO = 1 in terms of the very low frequency geared bending intermolecular vibration.

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Infrared spectra in the carbon monoxide CO stretch region (≈2150 cm−1) are assigned to the previously unobserved O-bonded form of the CO2-CO dimer (“isomer 2”), which has a planar T-shaped structure like that of the previously observed C-bonded form (“isomer 1”), but with the CO rotated by 180°. The effective center of mass intermolecular distances are 3.58 Å for isomer 2 as compared to 3.91 Å for isomer 1. In addition to the fundamental band, two combination bands are observed for isomer 2, yielding values for two intermolecular vibrational modes: 14.19 cm−1 for the in-plane CO bend and 22.68 cm−1 for the out-of-plane bend.

Infrared spectra in the carbon monoxide CO stretch region (∼2150 cm) and in the ν asymmetric stretch region of NO (∼2223 cm) are assigned to the previously unobserved O-bonded form of the CO-NO dimer ("isomer 2"). This van der Waals complex has a planar skewed T-shaped structure like that of the previously observed C-bonded form ("isomer 1"), but with the CO rotated by 180°. The effective intermolecular distance between the centers of mass is 3.51 Å for isomer 2 as compared to 3.88 Å for isomer 1. In addition to the fundamental band, two combination bands are observed for isomer 2, yielding values for two intermolecular vibrational modes: 14.502(5) cm for the coupled disrotatory motion or the uncoupled CO rock and 21.219(5) cm for the out-of-plane rock. We show that the published ab initio study on this system is inadequate in predicting the intermolecular frequencies for isomer 2 of CO-NO.

A high-resolution spectrum in the region of 2144 cm(-1) is assigned to the previously elusive CO trimer. In spite of interference from the CO dimer and some remaining unexplained details, there is strong evidence for a planar, cyclic, C-bonded trimer structure, with C(3h) symmetry and 4.42 Å intermolecular separation, in agreement with theoretical calculations. A modest vibrational blueshift of +0.85 cm(-1) is observed for the CO trimer, as compared to +0.71 cm(-1) for the C-bonded form of the dimer.

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