Thermochemistry of the smallest QOOH radical from the roaming fragmentation of energy selected methyl hydroperoxide ions
- Univ. of the Pacific, Stockton, CA (United States)
- Paul Scherrer Institute, Villigen (Switzerland)
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Here, the dissociative photoionization processes of methyl hydroperoxide (CH3OOH) have been studied by imaging Photoelectron Photoion Coincidence (iPEPICO) spectroscopy experiments as well as quantum-chemical and statistical rate calculations. Energy selected CH3OOH+ ions dissociate into CH2OOH+, HCO+, CH3+, and H3O+ ions in the 11.4–14.0 eV photon energy range. The lowest-energy dissociation channel is the formation of the cation of the smallest “QOOH” radical, CH2OOH+. An extended RRKM model fitted to the experimental data yields a 0 K appearance energy of 11.647 ± 0.005 eV for the CH2OOH+ ion, and a 74.2 ± 2.6 kJ mol-1 mixed experimental-theoretical 0 K heat of formation for the CH2OOH radical. The proton affinity of the Criegee intermediate, CH2OO, was also obtained from the heat of formation of CH2OOH+ (792.8 ± 0.9 kJ mol-1) to be 847.7 ± 1.1 kJ mol-1, reducing the uncertainty of the previously available computational value by a factor of 4. RRKM modeling of the complex web of possible rearrangement-dissociation processes was used to model the higher-energy fragmentation. Supported by Born–Oppenheimer molecular dynamics simulations, we found that the HCO+ fragment ion is produced through a roaming transition state followed by a low barrier. Lastly, H3O+ is formed in a consecutive process from the CH2OOH+ fragment ion, while direct C–O fission of the molecular ion leads to the methyl cation.
- Research Organization:
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE National Nuclear Security Administration (NNSA)
- Grant/Contract Number:
- AC04-94AL85000; NA0003525
- OSTI ID:
- 1485834
- Alternate ID(s):
- OSTI ID: 1462769
- Report Number(s):
- SAND-2018-12912J; PPCPFQ; 669829
- Journal Information:
- Physical Chemistry Chemical Physics. PCCP, Vol. 20, Issue 32; ISSN 1463-9076
- Publisher:
- Royal Society of ChemistryCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
Similar Records
A vacuum ultraviolet laser pulsed field ionization-photoion study of methane (CH4): Determination of the appearance energy of methylium from methane with unprecedented precision and the resulting impact on the bond dissociation energies of CH4 and CH4+
Gas-phase heats of formation of C sub 7 H sub 7 sup + isomers: M-tolyl, p-tolyl, and benzyl ions