Laser pulses with stable electric field waveforms establish the opportunity to achieve coherent control on attosecond time scales. We present experimental and theoretical results on the steering of electronic motion in a multielectron system. A very high degree of light-waveform control over the directional emission of C(+) and O(+) fragments from the dissociative ionization of CO was observed. Ab initio based model calculations reveal contributions to the control related to the ionization and laser-induced population transfer between excited electronic states of CO(+) during dissociation.

The steering of electron motion in molecules is accessible with waveform-controlled few-cycle laser light and may control the outcome of light-induced chemical reactions. An optical cycle of light, however, is much shorter than the duration of the fastest dissociation reactions, severely limiting the degree of control that can be achieved. To overcome this limitation, we extended the control metrology to the midinfrared studying the prototypical dissociative ionization of D(2) at 2.1 μm. Pronounced subcycle control of the directional D(+) ion emission from the fragmentation of D(2)(+) is observed, demonstrating unprecedented charge-directed reactivity. Two reaction pathways, showing directional ion emission, could be observed and controlled simultaneously for the first time. Quantum-dynamical calculations elucidate the dissociation channels, their observed phase relation, and the control mechanisms.

We review recent progress in the control over chemical reactions by employing tailored electric field waveforms of intense laser pulses. The sub-cycle tailoring of such waveforms permits the control of electron dynamics in molecules on sub-femtosecond timescales. We show that laser-driven electron dynamics in molecules has the potential to control chemical reactions. In the presence of strong fields, electron and nuclear motion are coupled, requiring models beyond the Born-Oppenheimer approximation for their theoretical treatment. Various mechanisms for the lightwave control of molecular reactions are described, and their relevance for the control of diatomic molecular reactions is discussed. Rapid experimental and theoretical progress is currently being made, indicating that attosecond controlled chemistry is within reach.

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.

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.

Strong few-cycle light fields with stable electric field waveforms allow controlling electrons on time scales down to the attosecond domain. We have studied the dissociative ionization of randomly oriented DCl in 5 fs light fields at 720 nm in the tunneling regime.

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We outline the details of our new method to calculate angular-dependent ionization probabilities based on electronic structure theory for diatomic and larger systems. To demonstrate its abilities, we compare our calculations to measured ionization probabilities of the four molecules D 2 , N 2 , O 2 and CO in the strong-field regime. The calculated angular distributions yield better agreement with the experimental data than those obtained from the widely used MO-ADK theory. For CO the measured angular distributions of ionic fragments indicate contributions to the ionization from both the HOMO and the HOMO-1 orbital, an effect that is addressed by the theory.