Infrared photochemistry of specifically deuterated bicyclopropyl. A direct test of statistical unimolecular rate theory applied to branching ratios in multiphoton dissociation
The infrared photochemical decomposition of bicyclopropyl-d/sub 4/, specifically deuterated on one ring, has been examined. The molecule incorporates two reactive moieties that are differentiated only by isotopic substitution, hydrogenated and deuterated cyclopropane rings. Since statistical theories predict essentially equivalent rates of decomposition of each ring at any internal energy, the branching ratio constitutes a direct probe for nonstatistical effects. From a determination of the deuterium distribution in the single-ring cleaved product, allylcyclopropane, a branching ratio, k/sub H//k/sub D/ = 1.03 +- 0.08, is calculated. This is in good agreement with the statistical prediction and provides direct chemical evidence for the lack of significant nonrandom chemistry in the multiphoton infrared photochemistry of bicyclopropyl under the conditions of these experiments. 6 figures, 1 table.
- Research Organization:
- Univ. of Minnesota, Minneapolis
- DOE Contract Number:
- AC02-80ER10592
- OSTI ID:
- 5433831
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 87:17
- Country of Publication:
- United States
- Language:
- English
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ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CONDENSED CYCLOALKANES
INFRARED SPECTRA
PHOTOLYSIS
DEUTERIUM
ISOTOPE EFFECTS
ALKENES
CHEMICAL REACTION YIELD
COMPARATIVE EVALUATIONS
DIENES
EXPERIMENTAL DATA
GAS CHROMATOGRAPHY
GASES
LABELLING
LASER RADIATION
MASS SPECTRA
MEDIUM VACUUM
NMR SPECTRA
PHOTOIONIZATION
PRESSURE DEPENDENCE
SAMPLE PREPARATION
STRUCTURAL CHEMICAL ANALYSIS
ALKANES
CHEMICAL REACTIONS
CHROMATOGRAPHY
CYCLOALKANES
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
FLUIDS
HYDROCARBONS
HYDROGEN ISOTOPES
INFORMATION
IONIZATION
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
POLYENES
RADIATIONS
SEPARATION PROCESSES
SPECTRA
STABLE ISOTOPES
YIELDS
400500* - Photochemistry
400302 - Organic Chemistry- Isotope Effects- (-1987)