Chemistry of hydrotrioxides. A comparative ab initio study of the equilibrium structures of monomeric and dimeric hydrotrioxides (CH3OOOH, H3SiOOOH) and hydroperoxides (CH3OOH, H3SiOOH). Relative bond strengths in and the gas phase acidities of hydrotrioxides and hydroperoxides

Ab initio calculations have been carried out to predict the equilibrium structures of monomeric and dimeric CH{sub 3}OOOH, H{sub 3}SiOOOH, CH{sub 3}OOH, and H{sub 3}SiOOH. The calculated relatively strong binding energies for the intermolecularly hydrogen-bonded cyclic dimers of the hydrotrioxides a...

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Bibliographic Details
Published in:Journal of the American Chemical Society 1990-03, Vol.112 (6), p.2124-2129
Main Authors: Koller, Joze, Hodoscek, Milan, Plesnicar, Bozo
Format: Article
Language:English
Subjects:
400201 - Chemical & Physicochemical Properties
Atomic and molecular physics
BINDING ENERGY
CALCULATION METHODS
CHALCOGENIDES
DIMERS
Electron correlation calculations for atoms and molecules
Electronic structure of atoms, molecules and their ions: theory
ENERGY
Exact sciences and technology
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
MATHEMATICAL MODELS
MOLECULAR ORBITAL METHOD
MOLECULAR STRUCTURE
OXIDES
OXYGEN COMPOUNDS
Physics
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Summary:Ab initio calculations have been carried out to predict the equilibrium structures of monomeric and dimeric CH{sub 3}OOOH, H{sub 3}SiOOOH, CH{sub 3}OOH, and H{sub 3}SiOOH. The calculated relatively strong binding energies for the intermolecularly hydrogen-bonded cyclic dimers of the hydrotrioxides and hydroperoxides investigated (BE = 6-8 kcal/mol) support the belief that self-association is the characteristic structural feature of these species. Ab initio calculations of the theoretical acidities, defined as the energy differences between the energy minima for the neutral molecules and those for the corresponding anions, reveal the following order of the gas-phase acidities: H{sub 3}SiOOOH > CH{sub 3}OOOH > H{sub 3}SiOOH > CH{sub 3}OOH. The investigation of relative bond strengths indicates that the RO-OOH bonds in the hydrotrioxides are weaker than the ROO-OH bonds, supporting the predictions from the previous thermochemical and kinetic studies that the split into RO{sm bullet} and {sm bullet}OOH radicals is the lowest energy radical decomposition pathway available for these polyoxides.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja00162a013