Time-dependent treatment of scattering: potential referenced and kinetic energy referenced modified Cayley approaches to atom–diatom collisions and time-scale separations

Abstract

. Can. J. Chem. 70, 686 (1992). The time-dependent Lippmann-Schwinger equation describing atom-diatom collisions is expressed in terms of a general reference Hamiltonian, H,, whose dynamics are easily solved in one representation, and a corresponding disturbance Hamiltonian, H,, whose dynamics are easily solved in a different representation. The wavefunction at time t + T is then expressed in terms of its value at a previous time r by means of a simple quadrature approximation. The resulting expression for +(t + T) has a form similar to that occurring in earlier numerical unitary solutions to the time-dependent Schrodinger equation via a Cayley transformation. The structure of the new equations is made explicit for (a) the choice where H , is taken to be the kinetic energy and H, is the potential energy and (b) the choice where H , is taken to be the potential energy and H, is the kinetic energy. In addition, we also deal with several alternatives for treating the binding potential of the diatom. Several alternatives for choosing representations are then explored for reducing the equations to a form amenable to computation. The short time structure of the equations is discussed in terms of a multiple time-scales analysis.Key words: molecular collisions, multiple time scales, quantum dynamics.