A multisurface DIM trajectory study of the reaction: O(1Dg)+H2(X 1Σ+g)→OH(X 2Π)+H(2S)

The diatomics‐in‐molecules method has been used to compute potential energy surfaces for the interactions between O(1Dg) atoms and hydrogen molecules, and a multisurface quasiclassical trajectory study of the reaction dynamics for collisions at several different reagent translational energies has been carried out using these potentials. The multisurface nature of the problem was explicitly included by using a surface‐hopping computational technique, based on Landau–Zener transition probabilities, which made all of the relevant surfaces available to the trajectory. The product energy distributions predicted by three slightly different DIM models of these surfaces are computed. In all cases, the dynamics of the reactions which begin on the first excited surface are dramatically different from those of reactions which occur on the lowest surface, the only one which was considered in all previous dynamical calculations on this system.

[1]  William H. Miller.  Dynamics of Molecular Collisions , 1976 .

[2]  S. Sibener,et al.  REACTIVE SCATTERING OF O(1D) + H2 , 1981 .

[3]  R. Polák,et al.  A sensitivity analysis of a diatomics-in-molecules model of the 1A' states of H2O , 1985 .

[4]  Yulin Huang,et al.  The nascent product vibrational energy distribution of the reaction O(1D)+H2 by the grating selection chemical laser technique , 1986 .

[5]  A. D. McLean,et al.  Extended basis first‐order CI study of the 1A′, 3A″, 1A″, and B̃ 1A′ potential energy surfaces of the O(3P,1D)+H2(1Σg+) reaction , 1979 .

[6]  J. Butler,et al.  Reaction dynamics of O(1D2)+H2, HD, D2: OH, OD(X 2Πi) product internal energy distributions , 1986 .

[7]  William A. Lester,et al.  Trajectory studies of O+H2 reactions on fitted abinitio surfaces. II. Singlet case , 1979 .

[8]  W. A. Payne,et al.  A flasch photolysis–resonance fluorescence study of the formation of O(1D) in the photolysis of water and the reaction of O(1D) with H2, Ar, and He − , 1975 .

[9]  D. Truhlar.  Potential Energy Surfaces and Dynamics Calculations , 1981 .

[10]  X. Chapuisat,et al.  An ab initio description of the excited states of the reaction O(3P, 1D) + H2 → OH(2Π, 2Σ+) + H. An attempt to describe several potential energy surfaces with constant accuracy , 1985 .

[11]  G. Schatz,et al.  A theoretical study of complex formation, isotope effects, and energy partitioning in the atomic oxygen(1D) + molecular hydrogen(D2, HD) reaction , 1986 .

[12]  P. Debye.  The Influence of Intramolecular Atomic Motion on Electron Diffraction Diagrams , 1941 .

[13]  L. Holmlid,et al.  Monte Carlo simulation of RRKM unimolecular decomposition in molecular beam experiments. I. Basic considerations and calculational procedure , 1981 .

[14]  J. J. Sloan,et al.  The initial product vibrational energy distribution in the reaction between O(1D2) and H2 , 1986 .

[15]  S. Carter,et al.  Approximate single-valued representations of multivalued potential energy surfaces , 1984 .

[16]  P. Whitlock,et al.  Quasiclassical trajectory investigation of the reaction O( 1D)+H2 , 1982 .

[17]  L. Holmlid,et al.  Monte carlo simulation of RRKM unimolecular decomposition in molecular beam experiments. IV. Product OH angular and velocity distributions from O(1D)+H2 , 1985 .

[18]  G. Paraskevopoulos,et al.  Competitive Reactions of the Excited Oxygen Atoms, O(1D)* , 1969 .

[19]  J. Butler,et al.  Vibrational excitation of OH(X2Π) produced in the reaction of O(1D) with H2 , 1983 .

[20]  Quasi-classical dynamics on the ground state surface of H2O , 1983 .

[21]  L. Holmlid,et al.  Monte Carlo simulation of RRKM unimolecular decomposition in molecular beam experiments. II. Application to angular distributions and absolute cross sections for the system K+RbCl , 1981 .

[22]  K. Sorbie,et al.  Theoretical study of the O(D) + H2(Sg ) reactive quenching process , 1976 .

[23]  G. Jursich,et al.  Abstraction versus insertion in the reaction O(1D2)+H2→OH(υ″ = 2) + H , 1985 .

[24]  James S. Wright,et al.  Abstraction vs insertion in O(1D)+H2→OH+H , 1982 .

[25]  W. Lester,et al.  Product state distributions in the reaction O(1D2)+H2→OH+H: Comparison of experiment with theory , 1979 .

[26]  I. Paidarová,et al.  Diatomics‐in‐molecules models for H2O and H2O−. II. A self‐consistent description of the 1A′, 1A″, 3A′, and 3A″ states of H2O , 1987 .

[27]  W. Demore.  Reaction of O(1D) with H2 and the Reactions of H and OH with Ozone , 1967 .

[28]  I. Paidarová,et al.  Diatomics‐in‐molecules models for H2O and H2O−. I. Valence bond diatomic fragment matrices , 1985 .

[29]  J. Butler,et al.  OH (X 2Πi) product internal energy distribution formed in the reaction of O(1D2) with H2 , 1980 .

[30]  G. Streit,et al.  Absolute rate constant determinations for the deactivation of O(1D) by time resolved decay of O(1D) →O(3P) emission , 1976 .

[31]  L. Holmlid,et al.  Monte Carlo simulation of O(1D) + H2 and O(1D) + HCl — rotational excitation of product OH radicals , 1985 .

[32]  J. Butler,et al.  The OH(X2Π, υ = 0) rotational energy distribution in the reaction of O(1D) + H2 , 1979 .

[33]  R. Bersohn,et al.  Isotopic branching ratio for the reaction A+HD→AD(H)+H(D) , 1985 .