Nonergodic behavior, possibly due to an insufficient density of states, in the decompositions of CH/sub 2/C(OH)OD/sup +/
Journal Article
·
· J. Phys. Chem.; (United States)
The metastable CH/sub 2/C(OH)OD/sup +/ ion loses OH and CH/sub 2/D via CH/sub 2/DCO/sub 2/H/sup +/ and CH/sub 3/ and OD via CH/sub 3/CO/sub 2/D/sup +/. About 3.7 kJ mol/sup -1/ (ca. 45%) more energy is released in the loss of OH than in the loss of OD, and less energy is released in the loss of CH/sub 2/D than of CH/sub 3/. The differing energy releases cannot be accounted for by isotopic influences on zero-point energies. It is concluded that energy is deposited differently in the intermediate acetic acid ions depending on whether H or D is transferred and that this difference is maintained and reflected in the subsequent fragmentations. Energy may remain localized because the fragmenting ions do not contain enough energy for the density of states to be high enough to permit energy randomization between isomerization and decomposition.
- Research Organization:
- Univ. of Texas, Galveston
- OSTI ID:
- 6492093
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 88:8; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
Similar Records
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Photoionization of CH/sub 3/OH, CD/sub 3/OH, and CH/sub 3/OD: Dissociative ionization mechanisms and ionic structures
Isotope exchange reactions of OH/sup -/ or OD/sup -/ with hydrogen and water
Journal Article
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Wed Aug 24 00:00:00 EDT 1994
· Journal of the American Chemical Society
·
OSTI ID:102764
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· J. Chem. Phys.; (United States)
·
OSTI ID:6920344
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Journal Article
·
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· J. Am. Chem. Soc.; (United States)
·
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
ACETIC ACID
ALCOHOLS
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
DEUTERIUM
ENERGY LEVELS
ENOLS
EXCITED STATES
EXPERIMENTAL DATA
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
INFORMATION
ISOTOPES
LABELLED COMPOUNDS
LIGHT NUCLEI
METASTABLE STATES
MONOCARBOXYLIC ACIDS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
STABLE ISOTOPES
THERMODYNAMICS
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
ACETIC ACID
ALCOHOLS
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
DEUTERIUM
ENERGY LEVELS
ENOLS
EXCITED STATES
EXPERIMENTAL DATA
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
INFORMATION
ISOTOPES
LABELLED COMPOUNDS
LIGHT NUCLEI
METASTABLE STATES
MONOCARBOXYLIC ACIDS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
STABLE ISOTOPES
THERMODYNAMICS