State-resolved thermalization of singlet and mixed singlet-triplet states of CH2.

The role of mixed states in the collision-induced thermalization, intersystem crossing, and reactive loss of CH(2) (~a (1)A1) has been monitored using Doppler-resolved transient frequency modulation absorption spectroscopy. Singlet CH(2) is produced in a hot initial distribution of translation and rotational energy states in the 308 nm photodissociation of ketene in a large excess of argon. Collisions with Ar and ketene cool the translational and rotational degrees of freedom, while depleting the total singlet CH(2) population through reaction and intersystem crossing.

Correlated product distributions from ketene dissociation measured by dc sliced ion imaging.

Speed distributions of spectroscopically selected CO photoproducts of 308 nm ketene photodissociation have been measured by dc sliced ion imaging. Structured speed distributions are observed that match the clumps and gaps in the singlet CH2 rotational density of states. The effects of finite time gates in sliced ion imaging are important for the accurate treatment of quasicontinuous velocity distributions extending into the thickly sliced and fully projected regime, and an inversion algorithm has been implemented for the special case of isotropic fragmentation.

Observation of the c1A1 state of methylene by optical-optical double resonance.

We report the observation of the rotationally resolved spectrum of the c1A1 state of CH2 via sequential single-photon absorptions at visible and near-infrared wavelengths. Direct absorption from the lowest singlet state a1A1 to c1A1 occurs in the near UV, but it is weak because it corresponds to a two electron transition between the dominant single configuration approximations to the electronic wave functions. Some absorption lines in the c-a system were originally reported in 1966 [G.

Electronic spectroscopy and ionization potential of UO2 in the gas phase.

The electronic spectroscopy of UO(2) has been examined using multiphoton ionization with mass-selected detection of the UO(2) (+) ions. Supersonic jet cooling was used to reduce the spectral congestion. Twenty-two vibronic bands of neutral UO(2) were observed in the range from 17,400 to 32,000 cm(-1).

Accurate ionization potentials for UO and UO2: a rigorous test of relativistic quantum chemistry calculations.

Accurate ionization potential (IP) measurements provide essential thermodynamic information and benchmark data that can be used to evaluate the validity of electronic structure models. Calculations of the first IP of UO2 using relativistic methods consistently predict values that are approximately 0.7 eV higher than the accepted experimental value.