Infrared laser single photon absorption reaction chemistry in the solid state. I. The system SiH/sub 4/--UF/sub 6/ a)
The reaction between SiH/sub 4/ and UF/sub 6/ under thermal gas phase and photon initiated conditions in cryogenic matrices has been investigated. The gas phase thermal reaction begins at 130--140/sup 0/ C producing HF, SiH/sub 3/F, and a solid uranium fluoride product. When the UF/sub 6/ is matrix isolated within SiH/sub 4/ at 12 K and exposed to low power infrared radiation of 25 mW cm/sup -2/ using laser emissions resonant with the ..nu../sub 3/ band of UF/sub 6/, a reaction also occurs. This reaction produces SiH/sub 3/F, UF/sub 5/, and UF/sub 4/ as products. The same reaction is also catalyzed using a broad band incoherent source with a photon flux density of 10 ..mu..W cm/sup -2/. The activation energy for the photoreaction (1.8 kcal mol/sup -1/) is considerably lower than the thermal activation barrier for the gas phase reaction. These experiments are part of the bases for uncovering a process of photochemistry of reactants in fixed relative configurations--single photon absorption reaction chemistry in the solid state (SPARCSS). This process is a manifestation of a previously unrecognized, general matrix phenomenon in which spatial configurations dramatically affect potential energy surfaces for reaction.
- Research Organization:
- Lawrence Livermore Laboratory, University of California, Livermore, California 94550
- OSTI ID:
- 6281367
- Journal Information:
- J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 70:7; ISSN JCPSA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Photoinduced reaction of UF/sub 6/ with SiH/sub 4/ in a low temperature SiH/sub 4/ matrix
Organic Materials Division. Quarterly report, January through March 1978. [SiH/sub 4/--UF/sub 6/]
Related Subjects
400500* -- Photochemistry
ACTINIDE COMPOUNDS
ACTIVATION ENERGY
CHEMISTRY
DATA
DATA FORMS
ELECTROMAGNETIC RADIATION
ENERGY
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
INFRARED RADIATION
ISOLATED VALUES
LASER RADIATION
NUMERICAL DATA
PHOTOCHEMISTRY
RADIATIONS
SILANES
SILICON COMPOUNDS
ULTRALOW TEMPERATURE
URANIUM COMPOUNDS
URANIUM FLUORIDES
URANIUM HEXAFLUORIDE