George M. Kramer

Isotope Selectivity of Infrared Laser-Driven Unimolecular Dissociation of a Volatile Uranyl Compound

Isotope-selective photodissociation of the volatile complex uranyl hexafluoroacetylacetonate � tetrahydrofuran [UO2(hfacac)2 � THF] has been achieved with both a continuous-wave and a pulsed carbon dioxide laser. The photodissociation was carried out in a low-density molecular beam under collisionless conditions. Transitions of the laser are in resonance with the asymmetric O-U-O stretch of the uranyl moiety, a vibrational mode whose frequency is sensitive to the masses of the uranium and oxygen isotopes. Unimolecular dissociation is observed mass spectrometrically at an extremely low energy fluence, with no evidence of an energy fluence or intensity threshold. The dissociation yield increases nearly linearly with increasing energy fluence. At constant fluence the dissociation yield is independent of contact time between the radiation field and the molecule, indicating that the decomposition is driven by laser energy fluence and not laser intensity. The oxygen and uranium isotope selectivities measured in these experiments are nearly those predicted by the ratio of the linear absorption cross sections for the respective isotopes. Thus, essentially complete selectivity is observed for oxygen isotopes, while a selectivity of only about 1.25 is measured for the uranium isotopes. A model presented to describe these results is based on rapid intramolecular vibrational energy flow from the pumped mode into a limited number of closely coupled modes.

Isotopic selectivity in the laser induced dissociation of molecules with overlapping absorption bands

Measurement of the isotopic selectivity as a function of temperature are described for IR laser induced dissociation of UO2(hfacac)2⋅THF in a low density molecular beam. The measured selectivity was found to increase from 1.2 at 120 °C to 1.9 at 65 °C. This behavior is consistent with a model which takes into account both the initial thermal energy content of the molecule and the energy barrier to dissociation. Indeed, such behavior is expected for any complex molecule which has isotopically shifted, but overlapping absorption spectra as is the case for the 235U and 238U containing molecules used in this study.

Catalysis of hydride transfer in strong acids

Abstract (A) Adamantane and several of its derivates have been found to catalyze intermolecular hydride transfer reactions. They function under a range of conditions from aprotic solutions of aluminum bromide in methylbromide to sulfuric acid.