Collinear classical dynamics on a chemically accurate H+H2 potential energy surface

Exchange in the hydrogen atom–molecule reaction is investigated via classical collinear dynamics on the Yates–Lester potential energy surface. A threshold kinetic energy of 6.4762 kcal/mole (0.2808 eV) is determined. Exchange probabilities are found to be, in general, slightly less than those obtained using the energy surface of Shavitt, Stevens, Minn, and Karplus. Energy banding is observed and discontinuities in the transition region are attributed to snarled trajectories. Reaction probabilities for all possible combinations of H, D, and T are determined. Isotopic variations in reaction probability are explained in terms of the mass‐dependent skew of the potential surface and differences in zero‐point vibrational energy.

[1]  K. Laidler,et al.  Energy bands in reactive collisions. I. H+H2 on the collinear SSMK surface , 1976 .

[2]  L. Raff,et al.  Comparison of quantum mechanical and quasiclassical scattering as a function of surface topology , 1976 .

[3]  J. Norbeck,et al.  Ab initio valence bond calculations of the potential energy surface for H+H2 , 1975 .

[4]  Robert E. Wyatt,et al.  Three‐dimensional natural coordinate asymmetric top theory of reactions: Application to H + H2 , 1975 .

[5]  K. Tang,et al.  Three‐dimensional quantum mechanical studies of D+H2→HD+H reactive scattering. II , 1975 .

[6]  R. Marcus,et al.  Semiclassical S matrix theory for a compound state resonance in the reactive collinear H + H2 collision , 1974 .

[7]  K. Tang,et al.  Theory of distorted‐wave Born approximation for reactive scattering of an atom and a diatomic molecule , 1974 .

[8]  P. Whitlock,et al.  Comparison of quasiclassical trajectory and classical S‐matrix treatments of collinear collisions of F and D2 , 1974 .

[9]  R. Porter.  Molecular Trajectory Calculations , 1974 .

[10]  D. Truhlar,et al.  Classical S matrix: numerical applications to classically allowed chemical reactions , 1974 .

[11]  W. Lester,et al.  A new H3 potential energy surface and its implications for chemical reaction , 1974 .

[12]  M. Karplus,et al.  Theoretical studies of H+H2 reactive scattering , 1974 .

[13]  D. Truhlar,et al.  Exact quantum mechanical reaction probabilities for the collinear H + H2 reaction on a porter-karplus potential energy surface☆ , 1973 .

[14]  G. Schatz,et al.  Role of direct and resonant (compound state) processes and of their interferences in the quantum dynamics of the collinear H + H2 exchange reaction , 1973 .

[15]  R. Levine,et al.  Application of semiclassical collision theory to the collinear reactive H+H2 system , 1973 .

[16]  J. Bowman,et al.  Comparison of semi-classical, exact quantum, and quasi-classical reactive transition probabilities for the collinear H + H2 reaction , 1973 .

[17]  Bowen Liu,et al.  Ab initio potential energy surface for linear H3 , 1973 .

[18]  R. Levine,et al.  Quantum mechanical computational studies of chemical reactions : II. Isotopic exchange reactions for the collinear H+H2 system , 1973 .

[19]  D. Hyatt,et al.  Reaction probabilities and high energy trajectories for collinear H−H2 collisions , 1972 .

[20]  D. J. Diestler,et al.  Effects of Variations of the Potential-Energy Surface on the Attributes of Simple Exchange Reactions: Classical Calculations , 1972 .

[21]  D. Truhlar,et al.  Exact and Approximate Quantum Mechanical Reaction Probabilities and Rate Constants for the Collinear H + H2 Reaction , 1972 .

[22]  M. Karplus,et al.  Comparison of Accurate Quantum‐Mechanical Probabilities with Classical and Transition‐State Theory Results for the Collinear Exchange Reaction H + H2 → H2 + H , 1971 .

[23]  J. Bowman,et al.  Classical and quantum reaction probabilities and thermal rate constants for the collinear H+H2 exchange reaction with vibrational excitation , 1971 .

[24]  R. Levine,et al.  Resonances in reactive collisions: Computational study of the H + H2 collision , 1971 .

[25]  M. Karplus,et al.  QUANTUM THEORY OF (H,H$sub 2$) SCATTERING: APPROXIMATE TREATMENTS OF REACTIVE SCATTERING. , 1971 .

[26]  C. Rankin,et al.  The Classical S-Matrix: Linear Reactive Collisions of H + Cl2 , 1971 .

[27]  M. Karplus,et al.  Differential Cross Sections for D+H2: A Comparison with Experiment , 1971 .

[28]  R. Marcus,et al.  Analytical Mechanics of Chemical Reactions. V. Application to the Linear Reactive H +H2 Systems , 1970 .

[29]  I. Shavitt.  Correlation of Experimental Rate Constants of the Hydrogen Exchange Reactions with a Theoretical H3 Potential Surface, Using Transition‐State Theory , 1968 .

[30]  E. Mortensen.  Classical Probabilities of Reaction and Transmission Coefficients for Isotopic Reactions of the Type H+H2=H2+H , 1968 .

[31]  Rudolph A. Marcus,et al.  Analytical Mechanics of Chemical Reactions. III. Natural Collision Coordinates , 1968 .

[32]  W. Kołos,et al.  Improved Theoretical Ground‐State Energy of the Hydrogen Molecule , 1968 .

[33]  V. McKoy,et al.  Quantum‐Mechanical Treatment of Inelastic Collisions. II. Exchange Reactions , 1968 .

[34]  C. E. Young,et al.  Energy Distribution Among Products of Exothermic Reactions. II. Repulsive, Mixed, and Attractive Energy Release , 1966 .

[35]  Martin Karplus,et al.  Dynamics of Reactive Collisions: The H +H2 Exchange Reaction , 1964 .

[36]  M. Karplus,et al.  Potential Energy Surface for H3 , 1964 .

[37]  F. T. Wall,et al.  Sensitivity of Exchange‐Reaction Probabilities to the Potential‐Energy Surface , 1963 .

[38]  R. E. Weston.  H3 Activated Complex and the Rate of Reaction of Hydrogen Atoms with Hydrogen Molecules , 1959 .

[39]  F. T. Wall,et al.  Statistical Computation of Reaction Probabilities. II , 1958 .

[40]  B. Stoicheff.  HIGH RESOLUTION RAMAN SPECTROSCOPY OF GASES: IX. SPECTRA OF H2, HD, AND D2 , 1957 .

[41]  L. Salem,et al.  Selection rules for classical reactive trajectories: Dynamical allowedness and forbiddenness , 1976 .

[42]  G. Schatz,et al.  Quantum initial conditions in quasi-classical trajectory calculations☆ , 1973 .

[43]  D. Silver.  Character of the Least‐Energy Trajectory near the Saddle‐Point on H3 Potential Surfaces , 1972 .

[44]  J. Muckerman.  Monte Carlo Calculations of Energy Partitioning and Isotope Effects in Reactions of Fluorine Atoms with H2, HD, and D2 , 1971 .

[45]  R. Levine,et al.  Quantum mechanical computational studies of chemical reactions: I. Close-coupling method for the collinear H + H2 reaction , 1971 .

[46]  H. Johnston.  Gas Phase Reaction Rate Theory , 1966 .

[47]  Samuel Glasstone,et al.  The Theory Of Rate Processes , 1941 .