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Optically centrifuged CO₂ molecules withJ= 244–282 are aligned with the excitation polarization while collision products with J= 76–100 have no polarization. Collisions relax〈m_J〉 at a rate of −2 per collision.

 

A combined experimental and theoretical study of quantum state-resolved rotational energy transfer kinetics of optically centrifuged CO molecules is presented. In the experiments, inverted rotational distributions of CO in rotational states up to J=80 were prepared using two different optical centrifuge traps, one with the full spectral bandwidth of the optical centrifuge pulses, and one with reduced bandwidth. The relaxation kinetics of the high-J tail of the inverted distribution from each optical trap was determined based on high-resolution transient IR absorption measurements. In parallel studies, master equation simulations were performed using state-to-state rate constants for CO-CO collisions in states up to J=90, based on data from double-resonance experiments for CO with J=0-29 and a fit to a statistical power exponential gap model. The model is in qualitative agreement with the observed relaxation profiles, but the observed decay rate constants are smaller than the simulated values by as much as a factor of 10. The observed decay rate constants also have a stronger J-dependence than predicted by the model. The results are discussed in terms of angular momentum and energy conservation, and compared to the observed orientational anisotropy decay kinetics of optically centrifuged CO molecules. Models for rotational energy transfer could be improved by including angular momentum effects. 

The effect of CO rotational energy on bimolecular reactions to form electronically excited C 2 is reported here. The reactions are initiated by CO multiphoton absorption of 800 nm light in strong optical fields using two different polarization configurations based on shaped chirped pulses. The observation of Swan band emission indicates that C 2 (d 3 Π g ) is a reaction product. The optical polarization is in the form of either an optical centrifuge or a dynamic polarization grating. In each case, the strong field aligns CO molecules and induces multiphoton absorption. Power-dependent measurements indicate at least seven photons are absorbed by CO; CO(a 3 Π) is a likely reactant candidate based on kinetic modeling. Relative reaction efficiencies are determined by measuring Swan band emission intensities. For a CO pressure of 100 Torr and an optical intensity of I = 2.0 × 10 13 W cm −2 , the relative C 2 (d 3 Π g ) yield with the dynamic polarization grating is twice that with the optical centrifuge. The extent of CO rotational energy was determined for both optical polarizations using high-resolution transient IR absorption for a number of CO states with J = 62–73 and E rot up to 10 400 cm −1 . Optical centrifuge excitation generates at least 2.5 times more rotationally excited CO molecules per quantum state than the dynamic polarization grating. The results indicate that the effect of large amounts of CO rotational energy is to reduce the yield of the C 2 products.