Infrared photochemistry of volatile uranyl complexes
The energy absorbed from a laser pulse by the volatile uranyl complex UO/sub 2/(HFA)/sub 2/TBPO (HFA = 1,1,1,5,5,5-hexafluoropentane-2,4-dionato ion; TBPO = tributylphosphine oxide), irradiated on the nu/sub 3/ asymmetric stretching frequency of the uranyl group, has been determined as a function of laser-pulse fluence and frequency. It was found that this large molecule (M/sub r/ = 902) can absorb in excess of 50 photons without undergoing any measurable decomposition and that the photon absorption is accompanied by a significant shift of the nu/sub 3/ absorption band. In a complementary study, the laser photochemistry of mixtures of U/sup 16/O/sup 16/O(HFA)/sub 2/TMP and U/sup 16/O/sup 18/O(HFA)/sub 2/TMP (TMP = trimethyl phosphate) was examined at laser fluences sufficiently high (0.4 to 1.1 J cm/sup -2/) to lead to the decomposition of the irradiated molecule. The nu/sub 3/ frequencies of the above species are separated by 17 cm/sup -1/, and isotope separation factors as high as 50 were obtained for the two molecules under certain experimental conditions using parallel beam geometries. Examination of the effects of the 16/18 to 16/16 ratio in the irradiated sample and of the effects of laser fluence and sample pressure suggests that the laser photochemistry of this system is dominated by collision-induced energy-transfer phenomena occurring after the laser pulse. 10 figures.
- Research Organization:
- Australian Atomic Energy Commission Research Establishment, Sydney
- OSTI ID:
- 6947788
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 86:13; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400203 -- Isotope Exchange & Isotope Separation-- (-1987)
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
COMPLEXES
DATA
DECOMPOSITION
DISPERSIONS
ELECTROMAGNETIC RADIATION
ESTERS
EVEN-EVEN NUCLEI
EXPERIMENTAL DATA
HIGH TEMPERATURE
INFORMATION
INFRARED SPECTRA
ISOTOPE EFFECTS
ISOTOPES
ISOTOPIC EXCHANGE
LABELLING
LASER RADIATION
LIGHT NUCLEI
MEDIUM VACUUM
MIXTURES
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
OXYGEN 18
OXYGEN ISOTOPES
PHOSPHORIC ACID ESTERS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PRESSURE DEPENDENCE
PULSE TECHNIQUES
RADIATIONS
SPECTRA
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
TBPO
TEMPERATURE DEPENDENCE
URANIUM COMPLEXES
URANYL COMPLEXES