Generalized path integral based quantum transition state theory

A theory for calculating rates of transitions in quantum systems is presented and applied to desorption of H from a 2 . Cu 110 surface. The quantum transition state is defined as a conical dividing surface in the space of closed Feynman paths and a 'reaction coordinate' in this extended space is used to parametrize a reversible work evaluation of the free energy barrier. In a low temperature, harmonic limit the theory reduces to instanton theory. Above the cross-over temperature for tunneling, the theory reduces to the centroid density approximation and in the classical limit, variational classical transition state theory is recovered. q 1997 Elsevier Science B.V.

[1]  W. Miller.  Semiclassical limit of quantum mechanical transition state theory for nonseparable systems , 1975 .

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

[3]  A. Stuchebrukhov.  Green's functions in quantum transition state theory , 1991 .

[4]  B. C. Garrett,et al.  Centroid‐density quantum rate theory: Variational optimization of the dividing surface , 1993 .

[5]  G. Voth,et al.  A path integral study of electronic polarization and nonlinear coupling effects in condensed phase proton transfer reactions , 1994 .

[6]  Gregory K. Schenter,et al.  A variational centroid density procedure for the calculation of transmission coefficients for asymmetric barriers at low temperature , 1995 .

[7]  Gillan.  Quantum simulation of hydrogen in metals. , 1988, Physical review letters.

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

[9]  Gill Mj,et al.  Quantum simulation of hydrogen in metals. , 1987 .

[10]  B. C. Garrett,et al.  Critical comparison of approximate and accurate quantum-mechanical calculations of rate constants for a model activated reaction in solution , 1992 .

[11]  B. C. Garrett,et al.  Quantum activated rate theory: Variational optimization of planar dividing surfaces , 1993 .

[12]  G. Voth,et al.  Rigorous formulation of quantum transition state theory and its dynamical corrections , 1989 .

[13]  R. Feynman,et al.  Quantum Mechanics and Path Integrals , 1965 .

[14]  A. Zichichi.  The Whys of Subnuclear Physics , 1979 .

[15]  Makarov,et al.  Quantum transition-state theory below the crossover temperature. , 1995, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.

[16]  Ian Affleck,et al.  Quantum Statistical Metastability , 1981 .

[17]  M J Gillan,et al.  Quantum-classical crossover of the transition rate in the damped double well , 1987 .

[18]  D. S. Makarov,et al.  Chemical Dynamics at Low Temperatures , 1994 .