The multiconfiguration time-dependent Hartree-Fock approach for the description of correlated few-electron dynamics in the presence of strong laser fields is introduced and a comprehensive description of the method is given. Total ionization and electron spectra for the ground and first excited ionic channels are calculated for one-dimensional model systems with up to six active electrons. Strong correlation effects are found in the shape of photoelectron peaks and the dependence of ionization on molecule size.

The first reported measurements of single attosecond pulses use laser dressed single-photon extreme ultraviolet (XUV) ionization of gas atoms. The determination of XUV pulse duration from the electron spectrum is based on a classical theory. Although classical models are known to give a qualitatively correct description of strong laser atom interaction, the validity must be scrutinized by a quantum-mechanical analysis. We establish a theoretical framework for the accurate temporal characterization of attosecond XUV pulses. Our analysis reveals an improved scheme that allows for direct experimental discrimination between single and multiple attosecond pulses.

Photoelectrons excited by extreme ultraviolet or x-ray photons in the presence of a strong laser field generally suffer a spread of their energies due to the absorption and emission of laser photons. We demonstrate that if the emitted electron wave packet is temporally confined to a small fraction of the oscillation period of the interacting light wave, its energy spectrum can be up- or downshifted by many times the laser photon energy without substantial broadening. The light wave can accelerate or decelerate the electron's drift velocity, i.e., steer the electron wave packet like a classical particle. This capability strictly relies on a sub-femtosecond duration of the ionizing x-ray pulse and on its timing to the phase of the light wave with a similar accuracy, offering a simple and potentially single-shot diagnostic tool for attosecond pump-probe spectroscopy.

Control over various fragmentation reactions of a series of polyatomic molecules (acetylene, ethylene, 1,3-butadiene) by the optical waveform of intense few-cycle laser pulses is demonstrated experimentally. We show both experimentally and theoretically that the responsible mechanism is inelastic ionization from inner-valence molecular orbitals by recolliding electron wave packets, whose recollision energy in few-cycle ionizing laser pulses strongly depends on the optical waveform. Our work demonstrates an efficient and selective way of predetermining fragmentation and isomerization reactions in polyatomic molecules on subfemtosecond time scales.

We experimentally and theoretically demonstrate a self-referenced wave-function retrieval of a valence-electron wave packet during its creation by strong-field ionization with a sculpted laser field. Key is the control over interferences arising at different time scales. Our work shows that the measurement of subcycle electron wave-packet interference patterns can serve as a tool to retrieve the structure and dynamics of the valence-electron cloud in atoms on a sub-10-as time scale.

We propose orthogonally polarized two-color laser pulses to steer tunneling electrons with attosecond precision around the ion core. We numerically demonstrate that the angles of birth and recollision, the recollision energy, and the temporal structure of the recolliding wave packet can be controlled without stabilization of the carrier-envelope phase of the laser, and that the wave packet's properties can be described by classical relations for a point charge. This establishes unique mapping between parameters of the laser field and attributes of the recolliding wave packet. The method is capable of probing ionic wave packet dynamics with attosecond resolution from an adjustable direction and might be used as an alternative to aligning molecules. Shaping the properties of the recollision wave packet by controlling the laser field may also provide new routes for improvement of attosecond pulse generation via high harmonic radiation.

Quantum tunneling is a ubiquitous phenomenon in nature and crucial for many technological applications. It allows quantum particles to reach regions in space which are energetically not accessible according to classical mechanics. In this "tunneling region," the particle density is known to decay exponentially. This behavior is universal across all energy scales from nuclear physics to chemistry and solid state systems. Although typically only a small fraction of a particle wavefunction extends into the tunneling region, we present here an extreme quantum system: a gigantic molecule consisting of two helium atoms, with an 80% probability that its two nuclei will be found in this classical forbidden region. This circumstance allows us to directly image the exponentially decaying density of a tunneling particle, which we achieved for over two orders of magnitude. Imaging a tunneling particle shows one of the few features of our world that is truly universal: the probability to find one of the constituents of bound matter far away is never zero but decreases exponentially. The results were obtained by Coulomb explosion imaging using a free electron laser and furthermore yielded He 2 's binding energy of 151.9 ± 13.3 neV, which is in agreement with most recent calculations.clusters | helium dimer | wavefunction | tunneling A ttractive forces allow particles to condense into stable bound systems such as molecules or nuclei with a ground state and (in most cases) energetically excited bound states, as shown in Fig. 1. Classical particles situated in such a binding potential oscillate back and forth between two turning points. The regions beyond these points are inaccessible for a classical particle due to a lack of energy. Quantum particles, however, can penetrate into the potential barrier by a phenomenon known as "tunneling." Tunneling is omnipresent in nature and occurs on all energy scales from megaelectron volts in nuclear physics to electron volts in molecules and solids and to nanoelectron volts in optical lattices. For bound matter, the fraction of the probability density distribution in this classically forbidden region is usually small. For shallow short-range potentials, this situation can change dramatically: upon decreasing the potential depth, excited states are expelled one after the other as they become unbound (transition from A to B in Fig. 1). A further decrease of the potential depth effects the ground state as well, as more and more of its wavefunction expands into the tunneling region ( Fig. 1 C and D). Consequently, at the threshold (i.e., in the limit of vanishing binding energy), the size of the quantum system expands to infinity. For short-range potentials, this expansion is accompanied by the fact that the system becomes less "classical" and more quantumlike. Systems existing near that threshold (and therefore being dominated by the tunneling part of their wavefunction) are called "quantum halo states" (1). These states are known, for example, from nuclear physics where 11 Be and 11 Li form ...

We test the multi-configuration time-dependent Hartree-Fock method as a new approach towards the numerical calculation of dynamical processes in multielectron systems using the harmonic quantum dot and one-dimensional helium in strong laser pulses as models. We find rapid convergence for quantities such as ground-state population, correlation coefficient and single ionization towards the exact results. The method converges, where the time-dependent Hartree-Fock method fails qualitatively.