Dynamics of O(3P) Reaction/Collision with Gaseous, Liquid, and Solid Hydrocarbons

  1. 1. Ab Initio Calculations of Potential Energy Surface Properties for O(3P) Processing of Hydrocarbon Materials.
  2. Electronic structure calculations were used to investigate a set of reactions relevant to O(3P) processing of hydrocarbon molecules and surfaces.1

fig1
Calculated TS structures of reactions (1)-(6) with CASSCF (CASPT2) [UMP2] and cc-pVTZ basis set.

  1. 2. A PM3-SRP + Analytic Function Potential Energy Surface Model for O(3P) Reactions with Alkanes.
  2. The PM3 semiempirical electronic structure theory was reparameterized with specific reaction parameters (SRPs) to develop a potential energy surface (PES) for O(3P) processing of alkanes.2

fig1
PM3-SRP + analytic functions fit to PMP2//UMP2/cc-pVTZ potential energy curve for O(3P) approaching CH4 in three different configurations. The PM3-SRP is model 2. The PM3 curves are shown for comparison.

  1. 3. A PM3-SRP Direct Dynamics Study of the O(3P) + C2H6 Reaction at the 5 eV Hyperthermal Collision Energy.
  2. The above PM3-SRP model was used in direct dynamics classical trajectory simulations of the O(3P) + C2H6 reaction at the 5 eV hyperthermal collision energy.2

fig1
Snapshots of four O(3P)+C2H6 reactive trajectories giving the products for channels 7, 11, 13 and 18.

  1. 4. Dynamics of Energy Transfer in Inelastic Collisions of O(3P) atoms with a 1-Decanethiol Self-Assembled Monolayer Surface.
  2. Chemical dynamics simulations were performed of energy transfer in collisions of O(3P) atoms with a 300 K 1-decanethiol self-assembled monolayer (H-SAM) surface.3

fig1
Bar graph of the fraction of the Boltzmann component in P(Ef), for different Ei and θi values. The temperature of the Boltzmann component, TB, does not equal 300K in the fit.

References

  1. 1. "Energetics, Transition States, and Intrinsic Reaction Coordinates for Reactions Associated with O(3P) Processing of Hydrocarbon Materials." Journal of Chemical Physics 120, 9253-9265 (2004)
    T.-Y. Yan, W. L. Hase and C. Doubleday
  2. 2. "A PM3-SRP + Analytic Function Potential Energy Surface Model for O(3P) Reactions with Alkanes. Application to O(3P) + Ethane." Journal of Physical Chemistry A 108, 9863-9875 (2004)
    T.-Y. Yan, C. Doubleday and W. L. Hase
  3. 3. "Dynamics of Energy Transfer in Collisions of O(3P) Atoms with a 1-Decanethiol Self-Assembled Monolayer Surface." Journal of Physical Chemistry B 110, 11863-11877 (2006)
    U. S. Tasić, T.–Y. Yan and W. L. Hase