Laser augmented decomposition. II. D/sub 3/BPF/sub 3/. [Deuterium effects]

Journal Article · Thu Jun 17 00:00:00 EDT 1976 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100554a004· OSTI ID:7156707

Chien, K R; Bauer, S H

The study of the accelerated decomposition of H/sub 3/BPF/sub 3/ induced by laser radiation (930-950 cm/sup -1/ was extended to the fully deuterated species. While in all essential respects the kinetics of the ir photolysis for the two compounds are identical, the few differences which were uncovered proved crucial in pointing to interesting features of the mechanism. These verified predictions were based on a normal mode analysis for the distribution of potential energy among the internal coordinates. For the laser augmented decomposition, E/sub a//sup L/ = 3.5 +- 1 kcal/mol, compared with E/sub a//sup th/ = 29.3 kcal/mol for the thermal process. The quantum efficiency is low, approximately 4 x 10/sup 4/ photons/molecule decomposed. The rates of decomposition depend on the isotopic content and are sensitively dependent on the frequency of the irradiating line. For example, with P(24) large fractionation ratios were found for D/sub 3/BPF/sub 3/ vs. H/sub 3/BPF/sub 3/, and small differences for D/sub 3//sup 11/BPF/sub 3/ vs. D/sub 3//sup 10/BPF/sub 3/. The levels of decomposition induced by the sequential three-photon absorption have been semiquantitatively accounted for.

• Research Organization: Cornell Univ., Ithaca, NY
• OSTI ID: 7156707
• Journal Information: J. Phys. Chem.; (United States), Vol. 80:13
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BORON COMPOUNDS
DECOMPOSITION
DEUTERIUM
ISOTOPE EFFECTS
PHOSPHORUS FLUORIDES
LASER RADIATION
CHEMICAL REACTIONS
ELECTROMAGNETIC RADIATION
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDROGEN ISOTOPES
ISOTOPES
LIGHT NUCLEI
NUCLEI
ODD-ODD NUCLEI
PHOSPHORUS COMPOUNDS
RADIATIONS
STABLE ISOTOPES
400202* - Isotope Effects
Isotope Exchange
& Isotope Separation