title: Potential Energy Surfaces for the Reactions of HO2Radical with CH2O and HO2in CO2Environment.
abstract: We report on potential energies for the transition state, reactant, and product complexes along the reaction pathways for hydrogen transfer reactions to hydroperoxyl radical from formaldehyde H2CO + HO2→ HCO + H2O2and another hydroperoxyl radical 2HO2→ H2O2+ O2in the presence of one carbon dioxide molecule. Both covalently bonded intermediates and weak intermolecular complexes are identified and characterized. We found that reactions that involve covalent intermediates have substantially higher activation barriers and are not likely to play a role in hydrogen transfer kinetics. The van der Waals complexation with carbon dioxide does not affect hydrogen transfer from formaldehyde, but it lowers the barrier for hydroperoxyl self-reaction by nearly 3 kcal/mol. This indicates that CO2environment is likely to have catalytic effect on HO2self-reaction, which needs to be included in kinetic combustion mechanisms in supercritical CO2.
authors.affiliation: National Research Nuclear University MEPhI , Kashirskoye shosse 31, Moscow 115409, Russia.
authors.forename: Artëm E
authors.initials: AE
authors.lastname: Masunov
authors.affiliation: Department of Chemistry and Biochemistry, 95 Chieftan Way Rm. 118 DLC, Florida State University , Tallahassee, Florida 32806, United States.
authors.forename: Arseniy A
authors.initials: AA
authors.lastname: Atlanov
authors.affiliation: Center for Advanced Turbomachinery and Energy Research (CATER), Mechanical and Aerospace Engineering, University of Central Florida , Orlando, Florida 32816, United States.
authors.forename: Subith S
authors.initials: SS
authors.lastname: Vasu