Semiclassical methods for nonseparable systems

Abstract

Semiclassical techniques have been widely used for describing the dynamics of molecular collisions. The calculation of discrete energy eigenvalue spectra in bound systems has also employed semiclassical methods. Work has been done toward developing semiclassical theories for rate constants in reactive systems and semiclassical eigenvalues in bound systems. Application of these theories have been made to nonseparable multidimensional systems. Transition-state theory has played an important role in chemical kinetics, and is very useful for approximating reaction rate constants for molecular systems. Many shortcomings of transition-state theory can be attributed to the assumption of separability of motion along the reaction coordinate. Semiclassical approximations have been made to the quantum rate expression, and the resulting semiclassical theory has been applied to the reactive H + H/sub 2/ system. Comparison of this nonseparable theory with quantum scattering calculations shows agreement which is quite good. Although the quantum condition for one-dimensional bound systems is well-known, generalization of these results to multidimensional nonseparable systems is not obvious. Work has been done toward a semiclassical quantum condition which is closest to the approach of Born. The Hamilton--Jacobi equation for the systems is solved in action--angle variables; in this way the classical Hamiltonian can be expressed as a function of action variables which are constants of motion for the system. Requiring the action variables to be integers provides the semiclassical eigenvalues. Numerical calculations have been performed on a two-dimensional coupled potential well with good agreement with the quantum eigenvalues. 18 figures, 6 tables.