Infrared photochemistry of specifically deuterated bicyclopropyl. A direct test of statistical unimolecular rate theory applied to branching ratios in multiphoton dissociation

Journal Article · Thu Aug 18 04:00:00 EDT 1983 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100240a010· OSTI ID:5433831

Farneth, W E; Thomsen, M W

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), Journal Name: J. Phys. Chem.; (United States) Vol. 87:17; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
400500* -- Photochemistry
ALKANES
ALKENES
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHROMATOGRAPHY
COMPARATIVE EVALUATIONS
CONDENSED CYCLOALKANES
CYCLOALKANES
DATA
DECOMPOSITION
DEUTERIUM
DIENES
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
FLUIDS
GAS CHROMATOGRAPHY
GASES
HYDROCARBONS
HYDROGEN ISOTOPES
INFORMATION
INFRARED SPECTRA
IONIZATION
ISOTOPE EFFECTS
ISOTOPES
LABELLING
LASER RADIATION
LIGHT NUCLEI
MASS SPECTRA
MEDIUM VACUUM
NMR SPECTRA
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOIONIZATION
PHOTOLYSIS
POLYENES
PRESSURE DEPENDENCE
RADIATIONS
SAMPLE PREPARATION
SEPARATION PROCESSES
SPECTRA
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
YIELDS