Air-photonics terahertz platform with versatile micro-controller based interface and data acquisition.

We present a terahertz (THz) platform employing air plasma produced by an ultrashort two-color laser pulse as a broadband THz source and air biased coherent detection (ABCD) of the THz field. In contrast to previous studies, a simple peak detector connected to a micro-controller board acquires the ABCD-signal coming from the avalanche photodiode. Numerical simulations of the whole setup yield temporal and spectral profiles of the terahertz electric field in both source and detection area. The latter ones are in excellent agreement with our measurements, confirming THz electric fields with peak amplitude in the MV/cm range. We further illustrate the capabilities of the platform by performing THz spectroscopy of water vapor and a polystyrene reference sample.

Electron correlation driven non-adiabatic relaxation in molecules excited by an ultrashort extreme ultraviolet pulse.

The many-body quantum nature of molecules determines their static and dynamic properties, but remains the main obstacle in their accurate description. Ultrashort extreme ultraviolet pulses offer a means to reveal molecular dynamics at ultrashort timescales. Here, we report the use of time-resolved electron-momentum imaging combined with extreme ultraviolet attosecond pulses to study highly excited organic molecules. We measure relaxation timescales that increase with the state energy. High-level quantum calculations show these dynamics are intrinsic to the time-dependent many-body molecular wavefunction, in which multi-electronic and non-Born-Oppenheimer effects are fully entangled. Hints of coherent vibronic dynamics, which persist despite the molecular complexity and high-energy excitation, are also observed. These results offer opportunities to understand the molecular dynamics of highly excited species involved in radiation damage and astrochemistry, and the role of quantum mechanical effects in these contexts.

Few-femtosecond passage of conical intersections in the benzene cation.

Observing the crucial first few femtoseconds of photochemical reactions requires tools typically not available in the femtochemistry toolkit. Such dynamics are now within reach with the instruments provided by attosecond science. Here, we apply experimental and theoretical methods to assess the ultrafast nonadiabatic vibronic processes in a prototypical complex system-the excited benzene cation. We use few-femtosecond duration extreme ultraviolet and visible/near-infrared laser pulses to prepare and probe excited cationic states and observe two relaxation timescales of 11 ± 3 fs and 110 ± 20 fs. These are interpreted in terms of population transfer via two sequential conical intersections. The experimental results are quantitatively compared with state-of-the-art multi-configuration time-dependent Hartree calculations showing convincing agreement in the timescales. By characterising one of the fastest internal conversion processes studied to date, we enter an extreme regime of ultrafast molecular dynamics, paving the way to tracking and controlling purely electronic dynamics in complex molecules.

Influence of long-range Coulomb interaction in velocity map imaging.

The standard velocity-map imaging (VMI) analysis relies on the simple approximation that the residual Coulomb field experienced by the photoelectron ejected from a neutral or ion system may be neglected. Under this almost universal approximation, the photoelectrons follow ballistic (parabolic) trajectories in the externally applied electric field, and the recorded image may be considered as a 2D projection of the initial photoelectron velocity distribution. There are, however, several circumstances where this approximation is not justified and the influence of long-range forces must absolutely be taken into account for the interpretation and analysis of the recorded images. The aim of this paper is to illustrate this influence by discussing two different situations involving isolated atoms or molecules where the analysis of experimental images cannot be performed without considering long-range Coulomb interactions. The first situation occurs when slow (meV) photoelectrons are photoionized from a neutral system and strongly interact with the attractive Coulomb potential of the residual ion. The result of this interaction is the formation of a more complex structure in the image, as well as the appearance of an intense glory at the center of the image. The second situation, observed also at low energy, occurs in the photodetachment from a multiply charged anion and it is characterized by the presence of a long-range repulsive potential. Then, while the standard VMI approximation is still valid, the very specific features exhibited by the recorded images can be explained only by taking into consideration tunnel detachment through the repulsive Coulomb barrier.

XUV-induced reactions in benzene on sub-10 fs timescale: nonadiabatic relaxation and proton migration.

Unraveling ultrafast dynamical processes in highly excited molecular species has an impact on our understanding of chemical processes such as combustion or the chemical composition of molecular clouds in the universe. In this article we use short (<7 fs) XUV pulses to produce excited cationic states of benzene molecules and probe their dynamics using few-cycle VIS/NIR laser pulses. The excited states produced by the XUV pulses lie in an especially complex spectral region where multi-electronic effects play a dominant role. We show that very fast τ ≈ 20 fs nonadiabatic processes dominate the relaxation of these states, in agreement with the timescale expected for most excited cationic states in benzene. In the CH3+ fragmentation channel of the doubly ionized benzene cation we identify pathways that involve structural rearrangement and proton migration to a specific carbon atom. Further, we observe non-trivial transient behavior in this fragment channel, which can be interpreted either in terms of propagation of the nuclear wavepacket in the initially excited electronic state of the cation or as a two-step electronic relaxation via an intermediate state.

XUV excitation followed by ultrafast non-adiabatic relaxation in PAH molecules as a femto-astrochemistry experiment.

Highly excited molecular species are at play in the chemistry of interstellar media and are involved in the creation of radiation damage in a biological tissue. Recently developed ultrashort extreme ultraviolet light sources offer the high excitation energies and ultrafast time-resolution required for probing the dynamics of highly excited molecular states on femtosecond (fs) (1 fs=10(-15) s) and even attosecond (as) (1 as=10(-18) s) timescales. Here we show that polycyclic aromatic hydrocarbons (PAHs) undergo ultrafast relaxation on a few tens of femtoseconds timescales, involving an interplay between the electronic and vibrational degrees of freedom. Our work reveals a general property of excited radical PAHs that can help to elucidate the assignment of diffuse interstellar absorption bands in astrochemistry, and provides a benchmark for the manner in which coupled electronic and nuclear dynamics determines reaction pathways in large molecules following extreme ultraviolet excitation.

Attosecond Hole Migration in Benzene Molecules Surviving Nuclear Motion.

Hole migration is a fascinating process driven by electron correlation, in which purely electronic dynamics occur on a very short time scale in complex ionized molecules, prior to the onset of nuclear motion. However, it is expected that due to coupling to the nuclear dynamics, these oscillations will be rapidly damped and smeared out, which makes experimental observation of the hole migration process rather difficult. In this Letter, we demonstrate that the instantaneous ionization of benzene molecules initiates an ultrafast hole migration characterized by a periodic breathing of the hole density between the carbon ring and surrounding hydrogen atoms on a subfemtosecond time scale. We show that these oscillations survive the dephasing introduced by the nuclear motion for a long enough time to allow their observation. We argue that this offers an ideal benchmark for studying the influence of hole migration on molecular reactivity.

Visualizing the coupling between red and blue stark states using photoionization microscopy.

In nonhydrogenic atoms in a dc electric field, the finite size of the ionic core introduces a coupling between quasibound Stark states that leads to avoided crossings between states that would otherwise cross. Near an avoided crossing, the interacting states may have decay amplitudes that cancel each other, decoupling one of the states from the ionization continuum. This well-known interference narrowing effect, observed as a strongly electric field-dependent decrease in the ionization rate, was previously observed in several atoms. Here we use photoionization microscopy to visualize interference narrowing in helium atoms, thereby explicitly revealing the mechanism by which Stark states decay. The interference narrowing allows measurements of the nodal patterns of red Stark states, which are otherwise not observable due to their intrinsic short lifetime.

Probing time-dependent molecular dipoles on the attosecond time scale.

Photoinduced molecular processes start with the interaction of the instantaneous electric field of the incident light with the electronic degrees of freedom. This early attosecond electronic motion impacts the fate of the photoinduced reactions. We report the first observation of attosecond time scale electron dynamics in a series of small- and medium-sized neutral molecules (N(2), CO(2), and C(2)H(4)), monitoring time-dependent variations of the parent molecular ion yield in the ionization by an attosecond pulse, and thereby probing the time-dependent dipole induced by a moderately strong near-infrared laser field. This approach can be generalized to other molecular species and may be regarded as a first example of molecular attosecond Stark spectroscopy.

Hydrogen atoms under magnification: direct observation of the nodal structure of Stark states.

To describe the microscopic properties of matter, quantum mechanics uses wave functions, whose structure and time dependence is governed by the Schrödinger equation. In atoms the charge distributions described by the wave function are rarely observed. The hydrogen atom is unique, since it only has one electron and, in a dc electric field, the Stark Hamiltonian is exactly separable in terms of parabolic coordinates (η, ξ, φ). As a result, the microscopic wave function along the ξ coordinate that exists in the vicinity of the atom, and the projection of the continuum wave function measured at a macroscopic distance, share the same nodal structure. In this Letter, we report photoionization microscopy experiments where this nodal structure is directly observed. The experiments provide a validation of theoretical predictions that have been made over the last three decades.

Single-size thermometric measurements on a size distribution of neutral fullerenes.

We present measurements of the velocity distribution of electrons emitted from mass-selected neutral fullerenes, performed at the intracavity free electron laser FELICE. We make use of mass-specific vibrational resonances in the infrared domain to selectively heat up one out of a distribution of several fullerene species. Efficient energy redistribution leads to decay via thermionic emission. Time-resolved electron kinetic energy distributions measured give information on the decay rate of the selected fullerene. This method is generally applicable to all neutral species that exhibit thermionic emission and provides a unique tool to study the stability of mass-selected neutral clusters and molecules that are only available as part of a size distribution.

Wave function microscopy of quasibound atomic states.

In the 1980s Demkov, Kondratovich, and Ostrovsky and Kondratovich and Ostrovsky proposed an experiment based on the projection of slow electrons emitted by a photoionized atom onto a position-sensitive detector. In the case of resonant excitation, they predicted that the spatial electron distribution on the detector should represent nothing else but a magnified image of the projection of a quasibound electronic state. By exciting lithium atoms in the presence of a static electric field, we present in this Letter the first experimental photoionization wave function microscopy images where signatures of quasibound states are evident. Characteristic resonant features, such as (i) the abrupt change of the number of wave function nodes across a resonance and (ii) the broadening of the outer ring of the image (associated with tunneling ionization), are observed and interpreted via wave packet propagation simulations and recently proposed resonance tunneling mechanisms. The electron spatial distribution measured by our microscope is a direct macroscopic image of the projection of the microscopic squared modulus of the electron wave that is quasibound to the atom and constitutes the first experimental realization of the experiment proposed 30 years ago.

Scaling laws for photoelectron holography in the midinfrared wavelength regime.

Midinfrared strong-field laser ionization offers the promise of measuring holograms of atoms and molecules, which contain both spatial and temporal information of the ion and the photoelectron with subfemtosecond temporal and angstrom spatial resolution. We report on the scaling of photoelectron holographic interference patterns with the laser pulse duration, wavelength, and intensity. High-resolution holograms for the ionization of metastable xenon atoms by 7-16 µm light from the FELICE free electron laser are presented and compared to semiclassical calculations that provide analytical insight.

Decay of C60 by delayed ionization and C2 emission: experiment and statistical modeling of kinetic energy release.

C(60) molecules highly excited in the nanosecond regime decay following ionization and dissociation by emitting a series of carbon dimers, as well as other small fragments if excitation is strong enough. The fragmentation mass spectrum and kinetic energy release of all charged fragments obtained in these experiments are interpreted within the framework of the Weisskopf theory, using a realistic Monte Carlo procedure in which the rates of all relevant decay channels are modeled using Arrhenius expressions. Comparison between the measurements and the simulated spectra allows the distribution of deposited energy to be accurately estimated. The dependence of the fragment kinetic energies on the laser fluence, found in the simulation but not observed in the experimental results, indicates that the small fragments are not necessarily emitted from small fullerenes resulting from C(60) by sequential decay. Rather, direct multifragmentation of C(60) is invoked to interpret the observed patterns. The possible role of post-ionization of neutral emitted fragments is discussed.

Combined electrospray ionization source with a velocity map imaging spectrometer for studying large gas phase molecular ions.

We present a new compact and versatile experimental set-up that has been designed to perform electron and ion imaging experiments on large multiply charged gas phase molecular and cluster species. It combines an electrospray ionization source, a quadrupole mass filter guiding ion optics and a velocity map imaging spectrometer. Characterization of the spectrometer has been performed on atomic ions. Results obtained on molecular species (stilbene 420 dianions) demonstrate the possibility offered by this experimental set-up.

Characterization of rhamnolipid production by Burkholderia glumae.

AIMS: To investigate if Burkholderia glumae can produce rhamnolipids, define a culture medium for good production yields, analyse their composition and determine their tensioactive properties. METHODS AND RESULTS: Burkholderia glumae AU6208 produces a large spectrum of mono- and di-rhamnolipid congeners with side chains varying between C(12)-C(12) and C(16)-C(16), the most abundant being Rha-Rha-C(14)-C(14).The effects on rhamnolipid production of the cultivation temperature, nitrogen and carbon source were investigated. With urea as the nitrogen source and canola oil as the carbon source, a production of 1000.7 mg l(-1) was reached after 6 days. These rhamnolipids display a critical micelle concentration of 25-27 mg l(-1) and decrease the interfacial tension against hexadecane from 40 to 1.8 mN m(-1). They also have excellent emulsifying properties against long chain alkanes. CONCLUSIONS: Burkholderia glumae AU6208 can produce considerable amounts of rhamnolipids. They are produced as diversified mixtures of congeners. Their side chains are longer than those normally produced by those of Pseudomonas aeruginosa. They also present excellent tensioactive properties. SIGNIFICANCE AND IMPACT OF THE STUDY: In contrast with the classical rhamnolipid producer Ps. aeruginosa, B. glumae is not a pathogen to humans. This work shows that the industrial production of rhamnolipids with this species could be easier than with Ps. aeruginosa.

Time-resolved holography with photoelectrons.

Ionization is the dominant response of atoms and molecules to intense laser fields and is at the basis of several important techniques, such as the generation of attosecond pulses that allow the measurement of electron motion in real time. We present experiments in which metastable xenon atoms were ionized with intense 7-micrometer laser pulses from a free-electron laser. Holographic structures were observed that record underlying electron dynamics on a sublaser-cycle time scale, enabling photoelectron spectroscopy with a time resolution of almost two orders of magnitude higher than the duration of the ionizing pulse.

Characterization of a two-color pump-probe setup at FLASH using a velocity map imaging spectrometer.

We report on the implementation of a high-count-rate charged particle imaging detector for two-color pump-probe experiments at the free electron laser in Hamburg (FLASH). In doing so, we have developed a procedure for finding the spatial and temporal overlap between the extreme UV free electron laser (FEL) pulses and the IR pulses, which allows for complete alignment of the setup in situations where the region of overlap between the FEL and the IR is not easily accessible by means of imaging optics.

Attosecond electron spectroscopy using a novel interferometric pump-probe technique.

We present an interferometric pump-probe technique for the characterization of attosecond electron wave packets (WPs) that uses a free WP as a reference to measure a bound WP. We demonstrate our method by exciting helium atoms using an attosecond pulse (AP) with a bandwidth centered near the ionization threshold, thus creating both a bound and a free WP simultaneously. After a variable delay, the bound WP is ionized by a few-cycle infrared laser precisely synchronized to the original AP. By measuring the delay-dependent photoelectron spectrum we obtain an interferogram that contains both quantum beats as well as multipath interference. Analysis of the interferogram allows us to determine the bound WP components with a spectral resolution much better than the inverse of the AP duration.

Electron localization following attosecond molecular photoionization.

For the past several decades, we have been able to directly probe the motion of atoms that is associated with chemical transformations and which occurs on the femtosecond (10(-15)-s) timescale. However, studying the inner workings of atoms and molecules on the electronic timescale has become possible only with the recent development of isolated attosecond (10(-18)-s) laser pulses. Such pulses have been used to investigate atomic photoexcitation and photoionization and electron dynamics in solids, and in molecules could help explore the prompt charge redistribution and localization that accompany photoexcitation processes. In recent work, the dissociative ionization of H(2) and D(2) was monitored on femtosecond timescales and controlled using few-cycle near-infrared laser pulses. Here we report a molecular attosecond pump-probe experiment based on that work: H(2) and D(2) are dissociatively ionized by a sequence comprising an isolated attosecond ultraviolet pulse and an intense few-cycle infrared pulse, and a localization of the electronic charge distribution within the molecule is measured that depends-with attosecond time resolution-on the delay between the pump and probe pulses. The localization occurs by means of two mechanisms, where the infrared laser influences the photoionization or the dissociation of the molecular ion. In the first case, charge localization arises from quantum mechanical interference involving autoionizing states and the laser-altered wavefunction of the departing electron. In the second case, charge localization arises owing to laser-driven population transfer between different electronic states of the molecular ion. These results establish attosecond pump-probe strategies as a powerful tool for investigating the complex molecular dynamics that result from the coupling between electronic and nuclear motions beyond the usual Born-Oppenheimer approximation.