Search

We demonstrate how the fast electron dynamics in molecules and hence the reaction of the system can be efficiently manipulated by controlling the temporal phase of an ultrashort laser pulse with attosecond precision.

The migration of hydrogen atoms resulting in the isomerization of hydrocarbons is an important process which can occur on ultrafast timescales. Here, we visualize the light-induced hydrogen migration of acetylene to vinylidene in an ionic state using two synchronized 4 fs intense laser pulses. The first pulse induces hydrogen migration, and the second is used for monitoring transient structural changes via Coulomb explosion imaging. Varying the time delay between the pulses reveals the migration dynamics with a time constant of 54 ± 4 fs as observed in the H + + H + + CC + channel. Due to the high temporal resolution, vibrational wave-packet motions along the CC- and CH-bonds are observed. Even though a maximum in isomerization yield for kinetic energy releases above 16 eV is measured, we find no indication for a backwards isomerization - in contrast to previous measurements. Here, we propose an alternative explanation for the maximum in isomerization yield, namely the surpassing of the transition state to the vinylidene configuration within the excited dication state.

The direct manipulation of charge oscillations has emerged as a new perspective in chemical reaction control. Here, we demonstrate, in a joint experimental and theoretical study, that the electron dynamics of a molecule is efficiently steered by controlling the interplay of a driving femtosecond laser pulse with the photoinduced charge oscillation. These oscillations have a typical Bohr period of around 1 fs for valence electrons; therefore, control has to be exerted on a shorter time scale. Specifically, we show how precision pulse shaping is used to manipulate the coupled electron and nuclear dynamics in order to address different bound electronic target states in a molecule. We present a strong-field coherent control mechanism which is understood in terms of a simple classical picture and at the same time verified by solving the time-dependent Schrödinger equation. This mechanism is universally applicable and opens a wide spectrum of applications in the reaction control of complex systems.

Optimal control theory and optimal control experiments are state-of-the-art tools to control quantum systems. Both methods have been demonstrated successfully for numerous applications in molecular physics, chemistry and biology. Modulated light pulses could be realized, driving these various control processes. Next to the control efficiency, a key issue is the understanding of the control mechanism. An obvious way is to seek support from theory. However, the underlying search strategies in theory and experiment towards the optimal laser field differ. While the optimal control theory operates in the time domain, optimal control experiments optimize the laser fields in the frequency domain. This also implies that both search procedures experience a different bias and follow different pathways on the search landscape. In this perspective we review our recent developments in optimal control theory and their applications. Especially, we focus on approaches, which close the gap between theory and experiment. To this extent we followed two ways. One uses sophisticated optimization algorithms, which enhance the capabilities of optimal control experiments. The other is to extend and modify the optimal control theory formalism in order to mimic the experimental conditions.