Dynamics in the excited ethylene cation C{sub 2}H{sub 4}{sup +} lead to isomerization to the ethylidene configuration (HC-CH{sub 3}){sup +}, which is predicted to be a transient configuration for electronic relaxation. With an intense femtosecond EUV (extreme ultraviolet) pump pulse to populate the excited state, and an NIR (near infrared) probe pulse to produce the fragments CH{sup +} and CH{sub 3}{sup +} (which provides a direct signature of ethylidene), we measure optimum fragment yields at a probe delay of 80 fs. Also, an H{sub 2}-stretch transient configuration, yielding H{sub 2}{sup +} upon probing, is found to succeed the ethylidene configuration. We find that a simple single- or double-decay model does not match the data, and we present a modified model (introduction of an isomerization delay of 50 {+-} 25 fs) that does provide agreement.

The Defense Waste Processing Facility at the Savannah River Site processes high-level radioactive waste from the processing of nuclear materials that contains dissolved and precipitated metals and radionuclides. Vitrification of this waste into borosilicate glass for ultimate disposal at a geologic repository involves chemically modifying the waste to make it compatible with the glass melter system. Pretreatment steps include removal of excess aluminum by dissolution and washing, and processing with formic and nitric acids to: (1) adjust the reduction-oxidation (redox) potential in the glass melter to reduce radionuclide volatility and improve melt rate; (2) adjust feed rheology; and (3) reduce by steam stripping the amount of mercury that must be processed in the melter. Elimination of formic acid pretreatment has been proposed to eliminate the production of hydrogen in the pretreatment systems; alternative reductants would be used to control redox. However, elimination of formic acid would result in significantly more mercury in the melter feed; the current specification is no more than 0.45 wt%, while the maximum expected prior to pretreatment is about 2.5 wt%. An engineering study has been undertaken to estimate the effects of eliminating mercury removal on the melter offgas system performance. A homogeneous gas-phase oxidation model …

Article on slow hydrogen atom transfer reactions of oxo- and hydroxo-vanadium compounds and the importance of intrinsic barriers.