A time‐dependent wave packet approach to atom–diatom reactive collision probabilities: Theory and application to the H+H2 (J=0) system

This paper describes a new approach to the study of atom–diatom reactive collisions in three dimensions employing wave packets and the time‐dependent Schrodinger equation. The method uses a projection operator approach to couple the inelastic and reactive portions of the total wave function and optical potentials to circumvent the necessity of using product arrangement coordinates. Reactive transition probabilities are calculated from the state resolved flux of the wave packet as it leaves the interaction region in the direction of the reactive arrangement channel. The wave packet does not need to be propagated into the asymptotic reactive region in order to determine accurate vibrationally resolved, but rotationally summed reaction probabilities. The present approach is used to obtain such vibrationally resolved reaction probabilities for the three‐dimensional H+H2 (J=0) hydrogen exchange reaction, using a body‐fixed system of coordinates.

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

[2]  J. Linderberg,et al.  Numerical implementation of reactive scattering theory , 1989 .

[3]  D. Neuhauser,et al.  Time dependent three‐dimensional body frame quantal wave packet treatment of the H+H2 exchange reaction on the Liu–Siegbahn–Truhlar–Horowitz (LSTH) surface , 1989 .

[4]  M. Baer,et al.  The time‐dependent Schrödinger equation: Application of absorbing boundary conditions , 1989 .

[5]  D. Neuhauser,et al.  Wave-packet approach to treat low energy reactive systems: accurate probabilities for hydrogen atom + hydrogen , 1989 .

[6]  M. Baer.  Arrangement channel approach to atom–diatom reactive systems: Theory and accurate three‐dimensional probabilities for the H+H2 system , 1989 .

[7]  David E. Manolopoulos,et al.  Quantum scattering via the log derivative version of the Kohn variational principle , 1988 .

[8]  G. Schatz.  Oscillating reactivity and resonances in the three-dimensional Cl+HCl reaction , 1988 .

[9]  E. Heller,et al.  Hybrid mechanics: A combination of classical and quantum mechanics , 1988 .

[10]  D. Kouri,et al.  Wave packet study of gas phase atom–rigid rotor scattering , 1988 .

[11]  V. Mohan,et al.  Quantal wavepacket calculations of reactive scattering , 1988 .

[12]  J. Launay,et al.  Three-dimensional quantum study of the reaction H+FH(νj)→HF(ν′j′)+H in hyperspherical coordinates , 1988 .

[13]  D. Kouri,et al.  L2 amplitude density method for multichannel inelastic and rearrangement collisions , 1988 .

[14]  W. Miller,et al.  New method for quantum reactive scattering, with applications to the 3-D H+H2 reaction , 1987 .

[15]  G. A. Parker,et al.  Quantum reactive scattering in three dimensions using hyperspherical (APH) coordinates. Theory , 1987 .

[16]  N. Sathyamurthy,et al.  Utility of the Sorbie-Murrell functional form in fitting the potential energy surface for the ground and the lowest excited state of triatomic hydrogen (H3) , 1987 .

[17]  H. Metiu,et al.  The dynamics of H2 dissociation on Ni(100): A quantum mechanical study of a restricted two‐dimensional model , 1987 .

[18]  Zhang,et al.  Wave-packet solution to the time-dependent arrangement-channel quantum-mechanics equations. , 1986, Physical review. A, General physics.

[19]  J. Manz,et al.  Mode selective dissociation of vibrationally excited ABA molecular resonances stimulated by a picosecond infrared laser pulse , 1986 .

[20]  A. Kuppermann,et al.  Three‐dimensional quantum mechanical reactive scattering using symmetrized hyperspherical coordinates , 1986 .

[21]  C. Leforestier.  Competition between dissociation and exchange processes in a collinear A + BC collision. I. Exact quantum results☆ , 1984 .

[22]  Ronnie Kosloff,et al.  A Fourier method solution for the time dependent Schrödinger equation: A study of the reaction H++H2, D++HD, and D++H2 , 1983 .

[23]  L. Raff,et al.  Calculation of reaction probabilities and rate coefficients for collinear three‐body exchange reactions using time‐dependent wave packet methods , 1981 .

[24]  D. Truhlar,et al.  Quasiclassical trajectory calculations and quantal wave packet calculations for vibrational energy transfer at energies above the dissociation threshold , 1980 .

[25]  G. Schatz,et al.  Quantum mechanical reactive scattering for planar atom plus diatom systems. I. Theory , 1976 .

[26]  D. Kouri,et al.  On the Lippmann–Schwinger equation for atom–diatom collisions: A rotating frame treatment , 1976 .

[27]  T. Kamal,et al.  Quantum mechanical investigations of the collinear collisions F + H2 and F + D2 using the wavepacket approach , 1975 .

[28]  R. Wyatt,et al.  Dynamics of the Collinear H+H2 Reaction. I. Probability Density and Flux , 1971 .

[29]  R. Rubin,et al.  Quantum‐Mechanical Calculation of the Probability of an Exchange Reaction for Constrained Linear Encounters , 1959 .

[30]  Yan Sun,et al.  Body frame close coupling wave packet approach to gas phase atom–rigid rotor inelastic collisions , 1989 .

[31]  J. Light,et al.  Atom-diatom reactive scattering. I. Quantum theory , 1989 .

[32]  D. Kouri,et al.  Quantum mechanical algebraic variational methods for inelastic and reactive molecular collisions , 1988 .

[33]  Michael Baer,et al.  Theory of chemical reaction dynamics , 1985 .

[34]  M. Feit,et al.  Solution of the Schrödinger equation by a spectral method II: Vibrational energy levels of triatomic molecules , 1983 .