Semiclassical initial value representation for electronically nonadiabatic molecular dynamics

The semiclassical initial value representation (SC-IVR), which has recently seen a great deal of interest for treating nuclear dynamics on a single potential energy surface, is generalized to be able to describe electronically nonadiabatic (i.e., multisurface) processes. The essential idea is a quantization of the classical electron-nuclear Hamiltonian of Meyer and Miller [J. Chem. Phys. 70, 3214 (1979)] within the SC-IVR methodology. Application of the approach to a series of test problems suggested by Tully shows it to provide a good description of electronically nonadiabatic dynamics for a variety of situations.

[1]  Fedor N. Dzegilenko,et al.  Recovering a full dimensional quantum rate constant from a reduced dimensionality calculation: Application to the OH+CO→H+CO2 reaction , 1996 .

[2]  H. C. Corben,et al.  Classical Mechanics (2nd ed.) , 1961 .

[3]  D. Coker,et al.  Methods for molecular dynamics with nonadiabatic transitions , 1994, chem-ph/9408002.

[4]  Michael F. Herman,et al.  Numerical comparison of generalized surface hopping, classical analog, and self-consistent eikonal approximations for nonadiabatic scattering , 1985 .

[5]  Richard A. Friesner,et al.  Stationary phase surface hopping for nonadiabatic dynamics: Two-state systems , 1994 .

[6]  Abraham Nitzan,et al.  Semiclassical evaluation of nonadiabatic rates in condensed phases , 1993 .

[7]  F. Strocchi,et al.  COMPLEX COORDINATES AND QUANTUM MECHANICS , 1966 .

[8]  R. Berry,et al.  Theory of Elementary Atomic and Molecular Processes in Gases , 1975 .

[9]  William H. Miller,et al.  Mixed semiclassical-classical approaches to the dynamics of complex molecular systems , 1997 .

[10]  W. Miller,et al.  Classical model for electronic degrees of freedom in nonadiabatic collision processes: Pseudopotential analysis and , 1979 .

[11]  W. Miller,et al.  Monte carlo integration with oscillatory integrands: implications for feynman path integration in real time , 1987 .

[12]  Mark A. Ratner,et al.  Time‐dependent self‐consistent field approximation for intramolecular energy transfer. I. Formulation and application to dissociation of van der Waals molecules , 1982 .

[13]  Michael F. Herman.  Generalization of the geometric optical series approach for nonadiabatic scattering problems , 1982 .

[14]  C. Zener.  Non-Adiabatic Crossing of Energy Levels , 1932 .

[15]  G. D. Billing,et al.  Semi-classical calculations of rotational/vibrational transitions in He-H2 , 1975 .

[16]  E. Heller.  Reply to Comment on: Semiclassical time evolution without root searches: Comments and perspective , 1991 .

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

[18]  W. Miller,et al.  Semiclassical Theory of Electronic Transitions in Low Energy Atomic and Molecular Collisions Involving Several Nuclear Degrees of Freedom , 1972 .