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

Abstract

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.

Phase- and intensity-dependence of ultrafast dynamics in hydrocarbon molecules in few-cycle laser fields

“…A large part of previous work was performed on molecular hydrogen and molecular hydrogen ions (see e.g. [8][9][10][11][12][13][14][15][16][17][18]). …”

Waveform control of orientation-dependent ionization of DCl in few-cycle laser fields

“…ref. [6][7][8][9][10] and references cited therein). The light-field induced electron localization leads to a directional emission of charged and uncharged fragments upon the break-up of the molecule.…”

Searching for pathways involving dressed states in optimal control theory

“…12,13 But in the case of the potassium dimer it turned out that the two sub-pulses have to overlap partially in time to ensure an efficient SPODS. 15 To explain their results, we used our approach for the coupled electron and nuclear quantum dynamics [17][18][19] and followed the time-dependent expectation value of the induced dipole moment along the molecular z-axis hm z i(t). The value of hm z i(t) is related to the time-dependent electron density 4 tot (t) 16 through: m z is the dipole operator along the intramolecular axis.…”