Vibrational energy distribution of CD/sub 2/(/sup 1/A/sub 1/) from ketene-d/sub 2/ photolysis upon reaction with cyclobutane. A chemically activated methylcyclobutane study

Journal Article · Thu May 09 00:00:00 EDT 1985 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100256a047· OSTI ID:5102834

Simons, J W; Mahone, W C

The results of a study of chemically activated methylcyclobutane and methylcyclobutane-d/sub 2/ from the 337-, 334-, and 313-nm photolyses of ketene or ketene-d/sub 2/ in the presence of cyclobutane, tetramethylsilane, and oxygen are presented. The collisional deactivation of the chemically activated molecules was found to occur in steps of 6 +/- 2 kcal/mol. A critical examination of the uncertainties in collisional deactivation stepsize determinations in chemical activation systems is given. The vibrational energy distribution of the CH/sub 2/(/sup 1/A/sub 1/) and CD/sub 2/(/sup 1/A/sub 1/) at the time of reaction with cyclobutane are determined and discussed. The distributions were found to broaden giving increasing average methylene energies with increasing photon energies and with deuterium substitution on the CH/sub 2/. An interesting quantum statistical isotope effect on the width of these distributions in going from the 337- to 313-nm photolysis systems is observed and explained in terms of the CH/sub 2/(/sup 1/A/sub 1/) and CD/sub 2/(/sup 1/A/sub 1/) vibrational frequency models. This is an energy partitioning isotope effect on CH/sub 2/CO vs. CD/sub 2/CO photodissociations. A statistical energy partitioning model for CH/sub 2/CO and CD/sub 2/CO photodissociation was found to give generally narrower methylene vibrational energy distributions and lower average energies than observed. 19 references, 10 figures, 6 tables.

• Research Organization: New Mexico State Univ., Las Cruces
• OSTI ID: 5102834
• Journal Information: J. Phys. Chem.; (United States), Vol. 89:10
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BUTANE
CHEMICAL REACTIONS
CYCLOALKANES
DEUTERIUM
KETENES
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
ACTIVATION ENERGY
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
ISOTOPE EFFECTS
MATHEMATICAL MODELS
MOLECULE-MOLECULE COLLISIONS
OXYGEN
RADICALS
SILANES
VIBRATIONAL STATES
ALKANES
COLLISIONS
DATA
DECOMPOSITION
ELEMENTS
ENERGY
ENERGY LEVELS
EXCITED STATES
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
LIGHT NUCLEI
MOLECULE COLLISIONS
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SILICON COMPOUNDS
SILICON COMPOUNDS
STABLE ISOTOPES
400500* - Photochemistry
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
400302 - Organic Chemistry- Isotope Effects- (-1987)