Transient IR spectroscopy of optically centrifuged CO2 (R186-R282) and collision dynamics for the J = 244-282 states.

Collisions of optically centrifuged CO2 molecules with J = 244-282 (Erot = 22 800-30 300 cm-1) are investigated with high-resolution transient IR absorption spectroscopy to reveal collisional and orientational phenomena of molecules with hyper-thermal rotational energies. The optical centrifuge is a non-resonant optical excitation technique that uses ultrafast, 800 nm chirped pulses to drive molecules to extreme rotational states through sequential Raman transitions. The extent of rotational excitation is controlled by tuning the optical bandwidth of the excitation pulses. Frequencies of 30 R-branch ν3 fundamental IR probe transitions are measured for the J = 186-282 states of CO2, expanding beyond previously reported IR transitions up to J = 128. The optically centrifuged molecules have oriented angular momentum and unidirectional rotation. Polarization-sensitive transient IR absorption of individual rotational states of optically centrifuged molecules and their collision products reveals information about collisional energy transfer, relaxation kinetics, and dynamics of rotation-to-translation energy transfer. The transient IR probe also measures the extent of polarization anisotropy. Rotational energy transfer for lower energy molecules is discussed in terms of statistical models and a comparison highlights the role of increasing energy gap with J and angular momentum of the optically centrifuged molecules.

Nanostructured CeO2 photocatalysts: optimizing surface chemistry, morphology, and visible-light absorption.

Emerging photocatalytic applications of cerium dioxide (CeO2) include green hydrogen production, CO2 conversion to fuels, and environmental remediation of various toxic molecules. These applications leverage the oxygen storage capacity and tunable surface chemistry of CeO2 to photocatalyze the chosen reaction, but many open questions remain regarding the fundamental physics of photocatalysis over CeO2. The commonly ascribed 'bandgap' of CeO2 (∼3.1 eV) differs fundamentally from other photocatalytic oxides such as TiO2; UV light excites an electron from the CeO2 valence band into a 4f state, generating a polaron as the lattice distorts around the localized charge. Researchers often disregard the distinction between the 4f state and a traditional, delocalized conduction band, resulting in ambiguity regarding mechanisms of charge transfer and visible-light absorption. This review summarizes modern literature regarding CeO2 photocatalysis and discusses commonly reported photocatalytic reactions and visible light-sensitization strategies. We detail the often misunderstood fundamental physics of CeO2 photocatalysis and supplement previous work with original computational insights. The exceptional progress and remaining challenges of CeO2-based photocatalysts are highlighted, along with suggestions for further research directions based on the observed gaps in current understanding.

Rotational energy transfer kinetics of optically centrifuged CO molecules investigated through transient IR spectroscopy and master equation simulations.

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.

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 Ttrans = 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.

The effect of CO rotation from shaped pulse polarization on reactions that form C2.

The effect of CO rotational energy on bimolecular reactions to form electronically excited C2 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 C2(d3Πg) 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(a3Π) 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 × 1013 W cm-2, the relative C2(d3Πg) 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 Erot 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 C2 products.