Kristina Meyer

Lorentz meets Fano in spectral line shapes: a universal phase and its laser control.

A Phase for Fano In spectroscopy, samples placed between a steady light source and a detector are characterized based on the relative intensities of light absorbed at different frequencies. Temporal behavior—the relaxation of a photoexcited state—can be indirectly inferred from the absorption band shapes. The advent of ultrafast laser technology has enabled increasingly sophisticated measurements directly in the time domain. Ott et al. (p. 716; see the Perspective by Lin and Chu) present an analytical framework to account for asymmetric band shapes, termed Fano profiles, on the basis of a phase shift in the temporal dipole response. An analytical framework bolstered by attosecond spectroscopy conveys a clear understanding of asymmetric spectral line shapes. [Also see Perspective by Lin and Chu] Symmetric Lorentzian and asymmetric Fano line shapes are fundamental spectroscopic signatures that quantify the structural and dynamical properties of nuclei, atoms, molecules, and solids. This study introduces a universal temporal-phase formalism, mapping the Fano asymmetry parameter q to a phase ϕ of the time-dependent dipole response function. The formalism is confirmed experimentally by laser-transforming Fano absorption lines of autoionizing helium into Lorentzian lines after attosecond-pulsed excitation. We also demonstrate the inverse, the transformation of a naturally Lorentzian line into a Fano profile. A further application of this formalism uses quantum-phase control to amplify extreme-ultraviolet light resonantly interacting with He atoms. The quantum phase of excited states and its response to interactions can thus be extracted from line-shape analysis, with applications in many branches of spectroscopy.

Reconstruction and control of a time-dependent two-electron wave packet

The concerted motion of two or more bound electrons governs atomic and molecular non-equilibrium processes including chemical reactions, and hence there is much interest in developing a detailed understanding of such electron dynamics in the quantum regime. However, there is no exact solution for the quantum three-body problem, and as a result even the minimal system of two active electrons and a nucleus is analytically intractable. This makes experimental measurements of the dynamics of two bound and correlated electrons, as found in the helium atom, an attractive prospect. However, although the motion of single active electrons and holes has been observed with attosecond time resolution, comparable experiments on two-electron motion have so far remained out of reach. Here we show that a correlated two-electron wave packet can be reconstructed from a 1.2-femtosecond quantum beat among low-lying doubly excited states in helium. The beat appears in attosecond transient-absorption spectra measured with unprecedentedly high spectral resolution and in the presence of an intensity-tunable visible laser field. We tune the coupling between the two low-lying quantum states by adjusting the visible laser intensity, and use the Fano resonance as a phase-sensitive quantum interferometer to achieve coherent control of the two correlated electrons. Given the excellent agreement with large-scale quantum-mechanical calculations for the helium atom, we anticipate that multidimensional spectroscopy experiments of the type we report here will provide benchmark data for testing fundamental few-body quantum dynamics theory in more complex systems. They might also provide a route to the site-specific measurement and control of metastable electronic transition states that are at the heart of fundamental chemical reactions.

Fractional high-order harmonic combs and energy tuning by attosecond-precision split-spectrum pulse control

We experimentally control high-order harmonic generation by applying a versatile few-cycle pulse-shape control method: splitting up a single broadband continuous laser spectrum into two sections and applying sub-femtosecond relative time delays. For certain time delays, fractional high-harmonic combs (noninteger harmonics) are generated which we find to result from the controlled interference of two attosecond pulse trains. We also observe time-delay-dependent energy-tunability of the high-order harmonics for an asymmetrically split spectrum consisting of a strong and a weak component. The tuning mechanism is quantitatively understood by the controlled modulation of the instantaneous driver frequency at the peak of the shaped laser pulse.

Noisy Optical Pulses Enhance the Temporal Resolution of Pump-Probe Spectroscopy

Time-resolved measurements of quantum dynamics are based on the availability of controlled events that are shorter than the typical evolution time scale of the processes to be observed. Here we introduce the concept of noise-enhanced pump-probe spectroscopy, allowing the measurement of dynamics significantly shorter than the average pulse duration by exploiting randomly varying, partially coherent light fields consisting of bunched colored noise. These fields are shown to be superior by more than a factor of 10 to frequency-stabilized fields, with important implications for time-resolved experiments at x-ray free-electron lasers and, in general, for measurements at the frontiers of temporal resolution (e.g., attosecond spectroscopy). As an example application, the concept is used to explain the recent experimental observation of vibrational wave-packet motion in D(2)(+) on time scales shorter than the average pulse duration.

Passively phase-stable, monolithic, all-reflective two-dimensional electronic spectroscopy based on a four-quadrant mirror.

A design for a passively phase-stable two-dimensional electronic spectroscopy experiment, based on a four-quadrant mirror concept, is introduced. The setup, which is particularly simple and robust, achieves subwavelength stability without the need for active stabilization or diffractive optical elements. Since only reflective optical components are used, the setup is suitable for few-cycle laser pulses and ultrabroad-bandwidth light in the ultraviolet, visible, and near-IR regions, with the capability to be used under grazing incidence for soft x ray or x-ray light at free-electron lasers.

Time-resolved four-wave-mixing spectroscopy for inner-valence transitions

Noncollinear four-wave-mixing (FWM) techniques at near-infrared (NIR), visible, and ultraviolet frequencies have been widely used to map vibrational and electronic couplings, typically in complex molecules. However, correlations between spatially localized inner-valence transitions among different sites of a molecule in the extreme ultraviolet (XUV) spectral range have not been observed yet. As an experimental step toward this goal, we perform time-resolved FWM spectroscopy with femtosecond NIR and attosecond XUV pulses. The first two pulses (XUV-NIR) coincide in time and act as coherent excitation fields, while the third pulse (NIR) acts as a probe. As a first application, we show how coupling dynamics between odd- and even-parity, inner-valence excited states of neon can be revealed using a two-dimensional spectral representation. Experimentally obtained results are found to be in good agreement with ab initio time-dependent R-matrix calculations providing the full description of multielectron interactions, as well as few-level model simulations. Future applications of this method also include site-specific probing of electronic processes in molecules.

Signatures and control of strong-field dynamics in a complex system

Significance Using intense lasers to control complex molecules is a long-held dream in science. In this article, we develop a physics concept for measuring and controlling the quantum states of complex molecules by strong laser fields. We show that, in particular, the quantum-mechanical phase of excited molecular states can be manipulated by the intense laser, a key quantity for full (amplitude and phase) control of molecular quantum states. With the help of time- and intensity-resolved absorption spectroscopy experiments, we apply this idea to the dynamics of a large dye molecule in solution. The demonstrated phase-control concept thus represents a major leap toward the ultimate goal of laser chemistry. Controlling chemical reactions by light, i.e., the selective making and breaking of chemical bonds in a desired way with strong-field lasers, is a long-held dream in science. An essential step toward achieving this goal is to understand the interactions of atomic and molecular systems with intense laser light. The main focus of experiments that were performed thus far was on quantum-state population changes. Phase-shaped laser pulses were used to control the population of final states, also, by making use of quantum interference of different pathways. However, the quantum-mechanical phase of these final states, governing the system’s response and thus the subsequent temporal evolution and dynamics of the system, was not systematically analyzed. Here, we demonstrate a generalized phase-control concept for complex systems in the liquid phase. In this scheme, the intensity of a control laser pulse acts as a control knob to manipulate the quantum-mechanical phase evolution of excited states. This control manifests itself in the phase of the molecule’s dipole response accessible via its absorption spectrum. As reported here, the shape of a broad molecular absorption band is significantly modified for laser pulse intensities ranging from the weak perturbative to the strong-field regime. This generalized phase-control concept provides a powerful tool to interpret and understand the strong-field dynamics and control of large molecules in external pulsed laser fields.

Characterization of Extreme Ultra-Violet Free-Electron Laser Pulses by Autocorrelation

We present EUV autocorrelation measurements of free-electron laser (FEL) pulses at 28 eV photon energy exploiting multiple ionization of argon as a non-linear process. In this way, the average pulse duration is measured while in parallel insight is gained into the temporal structure of the pulses. We compare the obtained results with FEL pulse simulations using our partial-coherence method (T. Pfeifer et al., Opt. Lett. 35:3441 (2010)).

Multiple ionization and fragmentation dynamics of molecular iodine studied in IR-XUV pump-probe experiments

The ionization and fragmentation dynamics of iodine molecules (I(2)) are traced using very intense (∼10(14) W cm(-2)) ultra-short (∼60 fs) light pulses with 87 eV photons of the Free-electron LASer at Hamburg (FLASH) in combination with a synchronized femtosecond optical laser. Within a pump-probe scheme the IR pulse initiates a molecular fragmentation and then, after an adjustable time delay, the system is exposed to an intense FEL pulse. This way we follow the creation of highly-charged molecular fragments as a function of time, and probe the dynamics of multi-photon absorption during the transition from a molecule to individual atoms.

Excited-State Phase Control In Strong Laser Fields: From Fundamental To Complex Systems

We measure and control the quantum-mechanical phase shift of excited quantum states using strong laser fields. This concept is demonstrated in gaseous helium and then generalized to a complex dye molecule in the liquid phase.