Electron attachment to volatile uranyl molecules

Journal Article · Fri Jan 01 00:00:00 EST 1982 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100394a008· OSTI ID:5261314

Yokozeki, A; Quitevis, E L; Herschbach, D R

Negative ion production by endoergic charge transfer from fast alkali atoms to a crossed molecular beam of uranyl complexes has been studied for three systems, UO/sub 2/L/sub 2/, UO/sub 2/L/sub 2/.THF, and UO/sub 2/L/sub 2/.TMP, where L denotes hexafluoroacetyacetonate, THF tetrahydrofuran, and TMP trimethyl phosphate. Near the lowest threshold, only negative ions of the parent molecules appear. The corresponding nominal electron affinities are 1.9 +/- 0.3, 1.6 +/- 0.2, and 1.5 +/- 0.3 eV, respectively. At higher collision energies, smaller negative ions appear, all containing the L/sup -/ anion; the variation with collision energy and source temperature indicates these come from dissociative electron attachment to the parent molecules rather than attahcment to products of thermal unimolecular decomposition. Qualitative electronic structure arguments suggest the attaching electron first enters a uranium 5f orbital and then migrates to the lowest vacant ..pi..* orbital of the L ligand.

• Research Organization: Harvard Univ., Cambridge, MA (United States)
• OSTI ID: 5261314
• Journal Information: J. Phys. Chem.; (United States), Vol. 86:5
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
URANYL COMPLEXES
PHOTOIONIZATION
STEREOCHEMISTRY
VOLATILITY
ACETYLACETONE
AFFINITY
CHARGE EXCHANGE
ELECTRON ATTACHMENT
EQUATIONS
EV RANGE
EXPERIMENTAL DATA
HIGH TEMPERATURE
MEDIUM TEMPERATURE
MOLECULE-MOLECULE COLLISIONS
POTENTIALS
SPECTRA
TETRAHYDROFURAN
THRESHOLD ENERGY
URANYL PHOSPHATES
ACTINIDE COMPLEXES
ACTINIDE COMPOUNDS
CHELATING AGENTS
COLLISIONS
COMPLEXES
DATA
ENERGY
ENERGY RANGE
FURANS
HETEROCYCLIC COMPOUNDS
INFORMATION
IONIZATION
KETONES
MOLECULE COLLISIONS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
PHOSPHATES
PHOSPHORUS COMPOUNDS
REAGENTS
URANIUM COMPLEXES
URANIUM COMPOUNDS
URANYL COMPOUNDS
400500* - Photochemistry
400702 - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials