Thermal and state‐selected rate constant calculations for O(3p) + H2 → OH + H and isotopic analogs

We present a new parametrization (based on ab initio calculations) of the bending potentials for the two lowest potential energy surfaces of the reaction O(3P) + H2, and we use it for rate constant calculations by variational transition-state theory with multidimensional semiclassical tunneling corrections. We present results for the temperature range 250–2400 K for both the rate constants and the intermolecular kinetic isotope effects for the reactions of O(3P) with D2 and HD. In general, the calculated rate constants for the thermal reactions are in excellent agreement with available experiments. We also calculate the enhancement effect for exciting H2 to the first excited vibrational state. The calculations also provide information on which aspects of the potential energy surfaces are important for determining the predicted rate constants.

[1]  D. C. Clary,et al.  The Theory of Chemical Reaction Dynamics , 1986 .

[2]  B. C. Garrett,et al.  A high‐barrier potential energy surface for F+H2→HF+H , 1985 .

[3]  B. C. Garrett,et al.  Variational transition state theory calculations of the reaction rates of F with H2, D2, and HD and the intermolecular and intramolecular kinetic isotope effects , 1985 .

[4]  B. C. Garrett,et al.  Effect of bending potential on calculated product‐state distributions for the reaction H+D2 → HD+D , 1985 .

[5]  J. Bowman,et al.  Inclusion and assessment of Renner–Teller coupling in transition state theory for Π states: Application to O(3P)+H2 , 1985 .

[6]  R. Gordon,et al.  The kinetic isotope effect in the reaction of O(3P) with H2, D2, and HD , 1985 .

[7]  Donald G. Truhlar,et al.  Improved canonical and microcanonical variational transition state theory calculations for a polyatomic reaction: OH+H2→H2O+H , 1985 .

[8]  F. B. Brown,et al.  An improved potential energy surface for F+H2→HF+H and H+H′F→HF+H′ , 1985 .

[9]  B. C. Garrett,et al.  Generalized transition state theory and least-action tunneling calculations for the reaction rates of atomic hydrogen(deuterium) + molecular hydrogen(n = 1) .fwdarw. molecular hydrogen(hydrogen deuteride) + atomic hydrogen , 1985 .

[10]  J. Bowman,et al.  Reaction dynamics for O(3P)+H2 and D2. IV. Reduced dimensionality quantum and quasiclassical rate constants with an adiabatic incorporation of the bending motion , 1984 .

[11]  B. C. Garrett,et al.  WKB approximation for the reaction‐path Hamiltonian: Application to variational transition state theory, vibrationally adiabatic excited‐state barrier heights, and resonance calculations , 1984 .

[12]  T. Carrington,et al.  Vinylidene: Potential energy surface and unimolecular reaction dynamics , 1984 .

[13]  D. Truhlar,et al.  Dependence of reaction attributes, including differential cross sections and resonance features, on changes in the potential energy surface for the F+D2 reaction , 1984 .

[14]  B. C. Garrett,et al.  Two new potential energy surfaces for the F+H2 reaction , 1984 .

[15]  D. Truhlar,et al.  Variational transition state theory calculations for an atom--radical reaction with no saddle point: O+OH , 1983 .

[16]  Donald G. Truhlar,et al.  Additions and Corrections - Generalized Transition State Theory. Quantum Effects for Collinear Reactions of Hydrogen Molecules , 1983 .

[17]  Donald G. Truhlar,et al.  Additions and Corrections - Incorporation of Quantum Effects in Generalized-Transition-State Theory , 1983 .

[18]  B. C. Garrett,et al.  Accurate calculations of the rate constants and kinetic isotope effects for tritium-substituted analogs of the atomic hydrogen + molecular hydrogen reaction , 1983 .

[19]  B. C. Garrett,et al.  Current status of transition-state theory , 1983 .

[20]  K. Westberg,et al.  Chemical Kinetic Data Sheets for High‐Temperature Chemical Reactions , 1983 .

[21]  B. C. Garrett,et al.  Test of variational transition state theory with a large‐curvature tunneling approximation against accurate quantal reaction probabilities and rate coefficients for three collinear reactions with large reaction‐path curvature: Cl+HCl, Cl+DCl, and Cl+MuCl , 1983 .

[22]  B. C. Garrett,et al.  Variational transition state theory and tunneling for a heavy–light–heavy reaction using an ab initio potential energy surface. 37Cl+H(D) 35Cl→H(D) 37Cl+35Cl , 1983 .

[23]  B. C. Garrett,et al.  Reaction-path interpolation models for variational transition state theory , 1983 .

[24]  B. C. Garrett,et al.  Quasiclassical trajectory (and variational transition state theory) study of the rates and temperature‐dependent activation energies of the reactions Mu+H2 (completely thermal) and H, D, and Mu+H2 (v=0, j=2) , 1983 .

[25]  B. C. Garrett,et al.  A least‐action variational method for calculating multidimensional tunneling probabilities for chemical reactions , 1983 .

[26]  B. C. Garrett,et al.  Vibrationally adiabatic models for reactive tunneling , 1982 .

[27]  D. Truhlar,et al.  Statistical‐diabatic model for state‐selected reaction rates. Theory and application of vibrational‐mode correlation analysis to OH(nOH)+H2(nHH)→H2O+H , 1982 .

[28]  B. C. Garrett,et al.  Kinetic isotope effects in the Mu+H2 and Mu+D2 reactions: Accurate quantum calculations for the collinear reactions and variational transition state theory predictions for one and three dimensions , 1982 .

[29]  G. Schatz,et al.  A comparative study of the reaction dynamics of several potential energy surfaces for O(3P)+H2 → OH+H. II. Collinear exact quantum and quasiclassical reaction probabilities , 1982 .

[30]  B. C. Garrett,et al.  New semiempirical method of modeling potential energy surfaces for generalized TST and application to the kinetic isotope effects in the Cl–H–H system , 1982 .

[31]  Donald G. Truhlar,et al.  Polyatomic canonical variational theory for chemical reaction rates. Separable‐mode formalism with application to OH+H2→H2O+H , 1982 .

[32]  G. B. Skinner,et al.  Resonance absorption measurements of atom concentrations in reacting gas mixtures. VIII. Rate constants for O+H2→OH+H and O+D2→OD+D from measurements of O atoms in oxidation of H2 and D2 by N2O , 1982 .

[33]  B. C. Garrett,et al.  Incorporation of quantum effects in generalized-transition-state theory , 1982 .

[34]  B. C. Garrett,et al.  A general small-curvature approximation for transition-state-theory transmission coefficients , 1981 .

[35]  R. Jaquet,et al.  Cepa calculations of potential energy surfaces for open-shell systems. I. The reaction of O(3P) with H2(1Σg+) , 1981 .

[36]  B. C. Garrett,et al.  Dynamical calculation of the temperature dependence of the activation energy for a chemical reaction from 444 to 2400 K , 1981 .

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

[38]  B. C. Garrett,et al.  Determination of the Bottleneck Regions of Potential Energy Surfaces for Atom Transfer Reactions by Variational Transition State Theory , 1981 .

[39]  A. Wagner,et al.  Theoretical Studies of Selected Reactions in the Hydrogen-Oxygen System , 1981 .

[40]  B. C. Garrett,et al.  Erratum: Generalized transition state theory. Quantum effects for collinear reactions of hydrogen molecules and isotopically substituted hydrogen molecules (The Journal of Physical Chemistry (1979) 83 (1079-1112)) , 1980 .

[41]  B. C. Garrett,et al.  Variational Transition State Theory , 1980 .

[42]  J. H. Matsumoto,et al.  Experimental measurement of the rate of the reaction o(3P) + H2(v = 0) OH(v = 0) + H at T = 298 K , 1980 .

[43]  Donald G. Truhlar,et al.  Comparison of variational transition state theory and the unified statistical model with vibrationally adiabatic transmission coefficients to accurate collinear rate constants for T+HD→TH+D , 1980 .

[44]  Donald G. Truhlar,et al.  Improved treatment of threshold contributions in variational transition-state theory , 1980 .

[45]  B. C. Garrett,et al.  Improved canonical variational theory for chemical reaction rates. Classical mechanical theory and applications to collinear reactions , 1980 .

[46]  Donald G. Truhlar,et al.  Generalized transition state theory calculations for the reactions D+H2 and H+D2 using an accurate potential energy surface: Explanation of the kinetic isotope effect , 1980 .

[47]  George C. Schatz,et al.  Theoretical studies of the O+H2 reaction , 1980 .

[48]  R. Raffenetti,et al.  A theoretical study of the potential energy surface for O(3P)+H2 , 1980 .

[49]  B. C. Garrett,et al.  Correction. Accuracy of Tunneling Corrections to Transition State Theory for Thermal Rate Constants of Atom Transfer Reactions , 1979 .

[50]  B. C. Garrett,et al.  Reliable ab initio calculation of a chemical reaction rate and a kinetic isotope effect: H + H(2) and H + H(2). , 1979, Proceedings of the National Academy of Sciences of the United States of America.

[51]  B. C. Garrett,et al.  Generalized transition state theory. Classical mechanical theory and applications to collinear reactions of hydrogen molecules , 1979 .

[52]  B. C. Garrett,et al.  Generalized transition state theory. Quantum effects for collinear reactions of hydrogen molecules and isotopically substituted hydrogen molecules , 1979 .

[53]  Donald G. Truhlar,et al.  Generalized transition state theory. Bond energy-bond order method for canonical variational calculations with application to hydrogen atom transfer reactions , 1979 .

[54]  Donald G. Truhlar,et al.  Importance of quartic anharmonicity for bending partition functions in transition-state theory , 1979 .

[55]  G. Light.  The effect of vibrational excitation on the reaction of O(3P) with H2 and the distribution of vibrational energy in the product OH , 1978 .

[56]  I. Campbell,et al.  Studies of reactions of atoms in a discharge flow stirred reactor. Part 3.—The O + H2+ O2 system , 1978 .

[57]  Michael E. Coltrin,et al.  A new tunneling path for reactions such as H+H2→H2+H , 1977 .

[58]  W. Miller.  Unified statistical model for ’’complex’’ and ’’direct’’ reaction mechanisms , 1976 .

[59]  D. J. Mckenney,et al.  Determination of the Rate Constant of the O + H2→OH + H Reaction using Atomic Oxygen Resonance Fluorescence and the Air Afterglow Techniques , 1975 .

[60]  D. Truhlar.  Multiple Potential Energy Surfaces for Reactions of Species in Degenerate Electronic States , 1972 .

[61]  D. Truhlar,et al.  A test of transition state theory against exact quantum mechanical calculations , 1971 .

[62]  D. Truhlar.  Adiabatic Theory of Chemical Reactions , 1970 .

[63]  A. A. Westenberg,et al.  Reinvestigation of the Rate Coefficients for O + H2 and O + CH4 , 1969 .

[64]  A. A. Westenberg,et al.  Atom—Molecule Kinetics Using ESR Detection. III. Results for O+D2→OD+D and Theoretical Comparison with O+H2→OH+H , 1967 .

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

[66]  R. Keyes.  An Antibonding Morse Potential , 1958, Nature.

[67]  S. Sato,et al.  Potential Energy Surface of the System of Three Atoms , 1955 .

[68]  S. Sato,et al.  On a New Method of Drawing the Potential Energy Surface , 1955 .