Bright circularly polarized soft X-ray high harmonics for X-ray magnetic circular dichroism.

We demonstrate, to our knowledge, the first bright circularly polarized high-harmonic beams in the soft X-ray region of the electromagnetic spectrum, and use them to implement X-ray magnetic circular dichroism measurements in a tabletop-scale setup. Using counterrotating circularly polarized laser fields at 1.3 and 0.79 µm, we generate circularly polarized harmonics with photon energies exceeding 160 eV. The harmonic spectra emerge as a sequence of closely spaced pairs of left and right circularly polarized peaks, with energies determined by conservation of energy and spin angular momentum. We explain the single-atom and macroscopic physics by identifying the dominant electron quantum trajectories and optimal phase-matching conditions. The first advanced phase-matched propagation simulations for circularly polarized harmonics reveal the influence of the finite phase-matching temporal window on the spectrum, as well as the unique polarization-shaped attosecond pulse train. Finally, we use, to our knowledge, the first tabletop X-ray magnetic circular dichroism measurements at the N4,5 absorption edges of Gd to validate the high degree of circularity, brightness, and stability of this light source. These results demonstrate the feasibility of manipulating the polarization, spectrum, and temporal shape of high harmonics in the soft X-ray region by manipulating the driving laser waveform.

Attosecond vacuum UV coherent control of molecular dynamics.

High harmonic light sources make it possible to access attosecond timescales, thus opening up the prospect of manipulating electronic wave packets for steering molecular dynamics. However, two decades after the birth of attosecond physics, the concept of attosecond chemistry has not yet been realized; this is because excitation and manipulation of molecular orbitals requires precisely controlled attosecond waveforms in the deep UV, which have not yet been synthesized. Here, we present a unique approach using attosecond vacuum UV pulse-trains to coherently excite and control the outcome of a simple chemical reaction in a deuterium molecule in a non-Born-Oppenheimer regime. By controlling the interfering pathways of electron wave packets in the excited neutral and singly ionized molecule, we unambiguously show that we can switch the excited electronic state on attosecond timescales, coherently guide the nuclear wave packets to dictate the way a neutral molecule vibrates, and steer and manipulate the ionization and dissociation channels. Furthermore, through advanced theory, we succeed in rigorously modeling multiscale electron and nuclear quantum control in a molecule. The observed richness and complexity of the dynamics, even in this very simplest of molecules, is both remarkable and daunting, and presents intriguing new possibilities for bridging the gap between attosecond physics and attochemistry.

Direct visualization of laser-driven electron multiple scattering and tunneling distance in strong-field ionization.

Using a simple model of strong-field ionization of atoms that generalizes the well-known 3-step model from 1D to 3D, we show that the experimental photoelectron angular distributions resulting from laser ionization of xenon and argon display prominent structures that correspond to electrons that pass by their parent ion more than once before strongly scattering. The shape of these structures can be associated with the specific number of times the electron is driven past its parent ion in the laser field before scattering. Furthermore, a careful analysis of the cutoff energy of the structures allows us to experimentally measure the distance between the electron and ion at the moment of tunnel ionization. This work provides new physical insight into how atoms ionize in strong laser fields and has implications for further efforts to extract atomic and molecular dynamics from strong-field physics.

Visualizing electron rearrangement in space and time during the transition from a molecule to atoms.

Imaging and controlling reactions in molecules and materials at the level of electrons is a grand challenge in science, relevant to our understanding of charge transfer processes in chemistry, physics, and biology, as well as material dynamics. Direct access to the dynamic electron density as electrons are shared or transferred between atoms in a chemical bond would greatly improve our understanding of molecular bonding and structure. Using reaction microscope techniques, we show that we can capture how the entire valence shell electron density in a molecule rearranges, from molecular-like to atomic-like, as a bond breaks. An intense ultrashort laser pulse is used to ionize a bromine molecule at different times during dissociation, and we measure the total ionization signal and the angular distribution of the ionization yield. Using this technique, we can observe density changes over a surprisingly long time and distance, allowing us to see that the electrons do not localize onto the individual Br atoms until the fragments are far apart (∼5.5 Å), in a region where the potential energy curves for the dissociation are nearly degenerate. Our observations agree well with calculations of the strong-field ionization rates of the bromine molecule.