Time-dependent quantum dynamics study of the Cl+H2 reaction

We report rigorous quantum dynamics studies of the Cl+H2 reaction. The time-dependent wave packet calculations are performed on the semiempirical G3 and the new BW2 potential energy surfaces. Initial state-specific total reaction probabilities and cross sections are calculated and the thermal rate constant is obtained. The quantum dynamics calculations show a striking difference in the energy dependence of reaction probabilities between the G3 and BW2 surfaces, with the former having a smaller reaction threshold. The calculated rate constant on the G3 surface is in good agreement with previous theoretical calculations at room temperature. The calculated rate constant on the new BW2 surface is smaller than that on the G3 surface, and comparison of them with experimental measurement is shown.

[1]  Hans-Joachim Werner,et al.  Global ab initio potential energy surfaces for the ClH2 reactive system , 2000 .

[2]  John C. Light,et al.  Quantum rate constants for the H2+OH reaction with the centrifugal sudden approximation , 1998 .

[3]  Wei Zhu,et al.  State‐to‐state time‐dependent quantum calculation for reaction H2+OH→H+H2O in six dimensions , 1996 .

[4]  John Z. H. Zhang,et al.  Quantum calculations of reaction probabilities for HO + CO→ H + CO2 and bound states of HOCO , 1995 .

[5]  A. Meijer,et al.  Time-dependent quantum mechanical calculations on H+O2 for total angular momentum J>0 , 1998 .

[6]  Dong H. Zhang,et al.  Full‐dimensional time‐dependent treatment for diatom–diatom reactions: The H2+OH reaction , 1994 .

[7]  G. Herzberg,et al.  Molecular Spectra and Molecular Structure , 1992 .

[8]  D. Truhlar,et al.  Dynamics of the Cl+H2/D2 reaction: a comparison of crossed molecular beam experiments with quasiclassical trajectory and quantum mechanical calculations , 2000 .

[9]  Yi Zhang,et al.  Quantum dynamics study of H2+CN → HCN+H reaction in full dimensions , 1998 .

[10]  B. C. Garrett,et al.  Variational transition state theory with least‐action tunneling calculations for the kinetic isotope effects in the Cl+H2 reaction: Tests of extended‐LEPS, information‐theoretic, and diatomics‐in‐molecules potential energy surfaces , 1985 .

[11]  Daniel Neuhauser,et al.  Fully quantal initial‐state‐selected reaction probabilities (J=0) for a four‐atom system: H2(v=0, 1, j=0)+OH(v=0,1, j=0)→H+H2O , 1994 .

[12]  Mark S. Gordon,et al.  AN IMPROVED POTENTIAL ENERGY SURFACE FOR THE H2CL SYSTEM AND ITS USE FOR CALCULATIONS OF RATE COEFFICIENTS AND KINETIC ISOTOPE EFFECTS , 1996 .

[13]  M. Baer.  Semiempirical three‐dimensional potential energy surfaces suitable for both reaction channels of the XH2 system (X = F, Cl) , 1981 .

[14]  R. Gordon,et al.  Kinetics of the Cl–H2 system. I. Detailed balance in the Cl+H2 reaction , 1981 .

[15]  John C. Light,et al.  Quantum state‐to‐state reaction probabilities for the H+H2O→H2+OH reaction in six dimensions , 1996 .

[16]  C. Kalyanaraman,et al.  Time-dependent quantum studies of the O(3P)+HCl(X 1Σ+) reaction , 1999 .

[17]  G. Schatz,et al.  Reduced-dimensionality quantum calculations of the thermal rate coefficient for the Cl+HCl→ClH+Cl reaction: Comparison with centrifugal-sudden distorted wave, coupled channel hyperspherical, and experimental results , 1990 .

[18]  Bian,et al.  van der waals interactions in the Cl + HD reaction , 1999, Science.

[19]  D. Manolopoulos,et al.  Time-dependent wave packet study of the N++H2 reaction , 1999 .

[20]  R. Weston.  Survey of reactions involving H', H'', and Cl atoms , 1979 .

[21]  Gillian C. Lynch,et al.  Ab Initio chemical kinetics: Converged quantal reaction rate constants for the D + H2 system , 1994 .

[22]  J. R. Morris,et al.  Time-dependent propagation of high energy laser beams through the atmosphere , 1976 .

[23]  R. Gordon,et al.  Kinetics of the Cl–H2 system. II. Abstraction vs exchange in D+HCl , 1983 .

[24]  L. Raff,et al.  A paradox: The thermal rate coefficient for the H+DCl --> HCl+D exchange reaction , 1975 .

[25]  John Z. H. Zhang,et al.  Quantum reactive scattering with a deep well: Time‐dependent calculation for H+O2 reaction and bound state characterization for HO2 , 1994 .

[26]  Dong H. Zhang,et al.  Accurate quantum calculation for the benchmark reaction H2+OH→H2O +H in five‐dimensional space: Reaction probabilities for J=0 , 1993 .

[27]  John Z. H. Zhang,et al.  DEVELOPMENT OF ACCURATE QUANTUM DYNAMICAL METHODS FOR TETRAATOMIC REACTIONS , 1997 .

[28]  F. B. Brown,et al.  Global potential-energy surfaces for H2Cl , 1989 .

[29]  G. Herzberg,et al.  Molecular Spectra and Molecular Structure: I. Spectra of Diatomic Molecules , 1944 .

[30]  S. Gray,et al.  Quantum dynamics with real wave packets, including application to three-dimensional (J=0) D + H2 → HD + H reactive scattering , 1998 .

[31]  Qinggang Zhang,et al.  Quantum wavepacket calculation for the ion molecule reaction N++H2→NH++H , 1999 .

[32]  Thomas C. Allison,et al.  Quantum Mechanical Rate Coefficients for the Cl + H2 Reaction , 1996 .

[33]  D. Neuhauser,et al.  The application of wave packets to reactive atom–diatom systems: A new approach , 1989 .

[34]  D. Truhlar,et al.  Dynamics of the Simplest Chlorine Atom Reaction: An Experimental and Theoretical Study , 1996, Science.

[35]  D. Neuhauser,et al.  A time‐dependent wave packet approach to atom–diatom reactive collision probabilities: Theory and application to the H+H2 (J=0) system , 1990 .

[36]  Wei Zhu,et al.  Quantum dynamics study of Li + HF reaction , 1997 .

[37]  Henry Eyring,et al.  The Absolute Rates of Reaction of Hydrogen with the Halogens , 1936 .

[38]  G. G. Balint-Kurti,et al.  Quantum mechanical three‐dimensional wavepacket study of the Li+HF→LiF+H reaction , 1996 .

[39]  R. Kosloff.  Time-dependent quantum-mechanical methods for molecular dynamics , 1988 .

[40]  Dong H. Zhang,et al.  Uniform J-shifting approach for calculating reaction rate constant , 1999 .

[41]  W. A. Payne,et al.  Absolute rate of the reaction of Cl(2P) with molecular hydrogen from 200–500 K , 1976 .

[42]  K. P. Lim,et al.  Thermal rate constants for the Cl+H2 and Cl+D2 reactions between 296 and 3000 K , 1994 .

[43]  Luis Bañares,et al.  Reaction Cross Sections and Rate Constants for the Cl + H2(D2) → HCl(DCl) + H(D) Reaction from Quasiclassical Trajectory Calculations on an ab Initio Potential Energy Surface , 1996 .

[44]  Nadia Balucani,et al.  Reactive scattering of atoms and radicals , 1995 .