Electron dynamics in molecules: a new combination of nuclear quantum dynamics and electronic structure theory

An efficient approach to describe electron dynamics in molecules is developed which exploits quantum dynamics and quantum chemistry in a new way. The photodissociation of D-2(+) which can be controlled via the carrier-envelope phase of an ultrashort laser pulse is chosen as a test system. In this system, the approach is checked against more rigorous theories as well as experiments which show excellent agreement. The electron dynamics is visualized in several ways including the phase information of the electronic wavefunction. The detailed analysis of the electron motion after different ionization events reveals the underlying complex dynamics which are hidden in the experiment. The interplay between the carrier-envelope phase and electron control is elucidated. The ansatz is based on the highly developed electronic structure theory and can be implemented quite easily. The method allows for a successive extension to multi-electron systems and simultaneously enables a quantum-dynamical description of the nuclear motion.