Time-dependent many-electron phenomena in quantum molecular dynamics

Abstract

An overview of work on electronic rearrangement in molecular collisions and in particular on combining time-dependent many-electron theory and eikonal methods for nuclear motions is presented. Special attention is given to the time scales present in atomic interactions with kinetic energies from a fraction of an eV to 10 keV, of interest in molecular collisions, atomic collisions with surfaces and transient spectra of electronically excited atoms in a medium. The treatment uses basis sets of travelling atomic orbitals, also adapted for the study of magnetic effects in molecules as gauge origin invariant atomic orbitals. An efficient computational approach to the time evolution of the systems, the relax-and-drive propagation method, is described. Brief descriptions are given of the connection with other approaches suitable for transient phenomena in molecular interactions.

Keywords:

• diabatic representation
• ionising collisions
• eikonal method
• time-dependent Hartee–Fock
• electronic density matrix
• time propagation algorithm
• electron transfer
• transient spectra
• He cluster

Acknowledgements

D.A. Micha thanks the National Science Foundation of the USA for support over many years and the Dreyfus Foundation for partial support.