State-resolved rotational distributions and collision dynamics of CO molecules made in a tunable optical centrifuge.

State-resolved distributions and collision dynamics of optically centrifuged CO molecules with orientated angular momentum are investigated by probing the CO J = 29-80 rotational levels using high-resolution transient IR absorption spectroscopy. An optical centrifuge with tunable bandwidth is used to control the extent of rotational excitation in the sample. The rotational distributions are inverted with a maximum population in J = 62. Rotational levels with J > 62 have populations that correlate with the intensity profile of the optical trap. The full bandwidth trap excites CO up to the J = 80 level, while J = 67 is the highest level observed in the reduced bandwidth trap. Polarization-sensitive transient spectroscopy shows that the initial orientational anisotropy is r = 0.8 for levels with J ≥ 55, while anisotropy values are near r = 0.4 for levels with J < 50. The rotational distribution for J > 50 is broadened slightly by collisions, consistent with small |ΔJ| propensity rules for rotational energy transfer. Doppler-broadened line profiles show that the J = 60-80 levels have translational temperatures near T = 300 K and that these temperatures remain constant for as much as 24 gas kinetic collisions. Doppler linewidths for levels with J < 60 are broadened by non-resonant rotation-to-translation energy transfer. Kinetic analysis of transient signals shows that collisions with thermal bath molecules are the predominant relaxation pathway.