Thermochemistry and dissociation dynamics of state-selection C/sub 4/H/sub 8/O/sub 2//sup +/ ions. 1. 1,4-dioxane

Journal Article · Fri Jan 01 00:00:00 EST 1982 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100394a031· OSTI ID:6786190

Fraser-Monteiro, M L ^[1]; Fraser-Monteiro, L; Butler, J J; Baer, T; Hass, J R

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1. Univ. of North Carolina, Chapel Hill

The photoionization efficiency curves and appearance energies for C/sub 4/H/sub 8/O/sub 2//sup +/, C/sub 3/H/sub 6/O/sup +/, C/sub 3/H/sub 5/O/sup +/, C/sub 2/H/sub 5/O/sup +/, C/sub 2/H/sub 4/O/sup +/ C/sub 2/H/sub 3/O/sup +/, CH/sub 3/O/sup +/, CH/sub 2/O/sup +/, CHO/sup +/, and C/sub 2/H/sub 4//sup +/ from 1,4-dioxane have been obtained. Structures and heats of formation for some of the ions are proposed. Fragment ion masses 44 (C/sub 2/H/sub 4/O/sup +/), 45 (C/sub 2/H/sub 5/O/sup +/) and 58 (C/sub 3/H/sub 6/O/sup +/) are the lowest energy dissociation products which appear at a photon energy of about 11.2 eV. All three ions are produced from long-lived (metastable) parent ions up to an energy of about 11.2 eV. The decay rates of internal energy selected parent ions were measured by photoion-photoelectron coincidence (PIPECO) and the results were compared to statistical theory (RRKM/QET) calculations. The three dissociation channels were found to be in competition with each other, and the data indicate that the dioxane ion does not isomerize to a more stable structure prior to dissociation. Kinetic energy release associated with the production of the m/e 58 fragment was measured as a function of the parent ion internal energy and found to be somewhat greater than that predicted by the statistical theory.

• OSTI ID: 6786190
• Journal Information: J. Phys. Chem.; (United States), Vol. 86:5
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DIOXANE
FRAGMENTATION
PHOTOIONIZATION
THERMODYNAMIC PROPERTIES
CATIONS
DECAY
DIAGRAMS
DISSOCIATION
DYNAMICS
EFFICIENCY
ENTHALPY
EXPERIMENTAL DATA
FREQUENCY ANALYSIS
ISOMERS
KINETIC ENERGY
MEDIUM TEMPERATURE
SPECTRA
STEREOCHEMISTRY
ULTRALOW TEMPERATURE
CHARGED PARTICLES
DATA
ENERGY
HETEROCYCLIC COMPOUNDS
INFORMATION
IONIZATION
IONS
MECHANICS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
400500* - Photochemistry
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)