Quasi-classical trajectory calculations of the thermal rate coefficient for the O + OH. -->. O/sub 2/ + H reaction on realistic double many-body expansion potential energy surfaces for ground-state HO/sub 2/

Journal Article · Thu Jul 28 04:00:00 EDT 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100326a059· OSTI ID:5993433

Quintales, L A.M.; Varandas, A J.C.; Alvarino, J M

Quasi-classical trajectory calculations of the thermal rate coefficient for the title reaction have been carried out over the temperature range 250 less than or equal to T less than or equal to 2500 K by using two recently reported DMBE potential energy surfaces for the ground state of the hydroperoxyl radical. The results are compared with each other and with experiment. The agreement is good. The authors results support previous theoretical calculations by Miller on the Melius-Blint potential energy surface in that nonstatistical recrossing effects are very important. For the DMBE II (DMBE III) potential energy surface, these nonstatistical corrections are found to increase from a factor of about 1.2 (1.4) at 250 K about 2.1 (2.5) at 2500 K. However, they are considerably smaller than the nonstatistical corrections reported by Miller (factors of about 2.2 and 3.3 at the above temperatures). Although due, of course, to topographical differences between the DMBE and Melius-Blint potential energy surfaces, such discrepancy stems also from the different definitions used for HO/sub 2/* complex in the simple chemical model O + OH /r reversible/ HO/sub 2/* ..-->.. O/sub 2/ + H.

• Research Organization: Universidade de Coimbra (Portugal)
• OSTI ID: 5993433
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:15; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
500100 -- Environment
Atmospheric-- Basic Studies-- (-1989)
54 ENVIRONMENTAL SCIENCES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
ELEMENTS
HYDROPEROXY RADICALS
HYDROXYL RADICALS
INFORMATION
KINETICS
NONMETALS
NUMERICAL DATA
OXYGEN
PHYSICAL PROPERTIES
RADICALS
REACTION KINETICS
TEMPERATURE DEPENDENCE
THEORETICAL DATA
THERMODYNAMIC PROPERTIES