Proton transfer and unimolecular decay in the low-energy-reaction dynamics of H/sub 3/O/sup +/ with acetone

Technical Report · Sat Jan 01 04:00:00 EST 1983

DOI:https://doi.org/10.2172/5758565· OSTI ID:5758565

Creasy, W R; Farrar, J M

The title reaction has been studied at collision energies of 0.83 and 2.41 eV. Direct reaction dynamics have been observed at both energies and an increasingly high fraction of the total energy appears in product translation as the collision energy increases. This result is consistent with the concept of induced repulsive energy release, which becomes more effective as trajectories sample the corner of the potential energy surface. At the higher collision energy, the protonated acetone cation undergoes two unimolecular decay channels: C-C bond cleavage to CH/sub 3/CO/sup +/ and CH/sub 4/, and C-O bond cleavagto C/sub 3/H/sub 5//sup +/ (presumably to allyl cation) and H/sub 2/O. The CH/sub 3/CO/sup +/ channel, endothermic relative to ground state protonated acetone cations by 0.74 eV, appears to liberate 0.4 eV in relative product translation while the C/sub 3/H/sub 5//sup +/ channel, endothermic by 2.17 eV, liberates only 0.07 eV in relative translation. These results are discussed in terms of the location on the reaction coordinate and magnitudes of potential energy barriers to 1,3-hydrogen atoms shifts which must precede the bond cleavage processes.

• Research Organization: Rochester Univ., NY (USA). Dept. of Chemistry
• Sponsoring Organization: USDOE
• DOE Contract Number: AC02-78ER04694
• OSTI ID: 5758565
• Report Number(s): DOE/ER/04694-T2; ON: DE84000471
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ACETONE
CATIONS
CHARGED PARTICLES
COLLISIONS
DISSOCIATION
ENERGY RANGE
EV RANGE
ION COLLISIONS
ION-MOLECULE COLLISIONS
IONS
KETONES
MOLECULAR IONS
MOLECULE COLLISIONS
ORGANIC COMPOUNDS
OXONIUM IONS