Quantum-classical dynamics of scattering processes in adiabatic and diabatic representations.

We demonstrate the workability of a TDDVR based [J. Chem. Phys. 118, 5302 (2003)], novel quantum-classical approach, for simulating scattering processes on a quasi-Jahn–Teller model [J. Chem. Phys. 105, 9141 (1996)] surface. The formulation introduces a set of DVR grid points defined by the Hermite part of the basis set in each dimension and allows the movement of grid points around the central trajectory. With enough trajectories (grid points), the method converges to the exact quantum formulation whereas with only one grid point, we recover the conventional molecular dynamics approach. The time-dependent Schrödinger equation and classical equations of motion are solved self-consistently and electronic transitions are allowed anywhere in the configuration space among any number of coupled states. Quantum-classical calculations are performed on diabatic surfaces (two and three) to reveal the effects of symmetry on inelastic and reactive state-to-state transition probabilities, along with calculations on an adiabatic surface with ordinary Born–Oppenheimer approximation. Excellent agreement between TDDVR and DVR results is obtained in both the representations. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]