Cristian Sarpe

Circular Dichroism in the Photoelectron Angular Distributions of Camphor and Fenchone from Multiphoton Ionization with Femtosecond Laser Pulses

Shine a light: a circular dichroism effect in the ±10 % regime on randomly oriented chiral molecules in the gas phase is demonstrated. The signal is derived from images of photoelectron angular distributions produced by resonance-enhanced multiphoton ionization and allows the enantiomers to be distinguished. To date, this effect could only be generated with a synchrotron source. The new tabletop laser-based approach will make this approach far more accessible.

Zeptosecond precision pulse shaping.

We investigate the temporal precision in the generation of ultrashort laser pulse pairs by pulse shaping techniques. To this end, we combine a femtosecond polarization pulse shaper with a polarizer and employ two linear spectral phase masks to mimic an ultrastable common-path interferometer. In an all-optical experiment we study the interference signal resulting from two temporally delayed pulses. Our results show a 2σ-precision of 300 zs = 300 × 10(-21) s in pulse-to-pulse delay. The standard deviation of the mean is 11 zs. The obtained precision corresponds to a variation of the arms length in conventional delay stage based interferometers of 0.45 Å. We apply these precisely generated pulse pairs to a strong-field quantum control experiment. Coherent control of ultrafast electron dynamics via photon locking by temporal phase discontinuities on a few attosecond timescale is demonstrated.

Spatio-temporal resolution studies on a highly compact ultrafast electron diffractometer

Time-resolved diffraction with femtosecond electron pulses has become a promising technique to directly provide insights into photo induced primary dynamics at the atomic level in molecules and solids. Ultrashort pulse duration as well as extensive spatial coherence are desired, however, space charge effects complicate the bunching of multiple electrons in a single pulse. We experimentally investigate the interplay between spatial and temporal aspects of resolution limits in ultrafast electron diffraction (UED) on our highly compact transmission electron diffractometer. To that end, the initial source size and charge density of electron bunches are systematically manipulated and the resulting bunch properties at the sample position are fully characterized in terms of lateral coherence, temporal width and diffracted intensity. We obtain a so far not reported measured overall temporal resolution of 130 fs (full width at half maximum) corresponding to 60 fs (root mean square) and transversal coherence lengths up to 20 nm. Instrumental impacts on the effective signal yield in diffraction and electron pulse brightness are discussed as well. The performance of our compact UED setup at selected electron pulse conditions is finally demonstrated in a time-resolved study of lattice heating in multilayer graphene after optical excitation.

Real-time observation of transient electron density in water irradiated with tailored femtosecond laser pulses

Ionization mechanisms in water irradiated with bandwidth-limited and temporally asymmetric femtosecond laser pulses are investigated via ultrafast spectral interferometry. By using a novel common-path interferometer with an enlarged temporal measurement window, we directly observe the dynamics of free-electron plasma generated by shaped pulses. We found that a temporally asymmetric pulse and its time-reversed counterpart address multiphoton and avalanche ionization mechanisms in a different fashion. Positive third-order dispersion shaped pulses produce a much higher free-electron density than negative ones at the same fluence, instantaneous frequency and focusing conditions. From the experimental data obtained after irradiation with bandwidth-limited and shaped pulses the multiphoton and avalanche coefficients were determined using a generic rate equation. We conclude that temporal tailored femtosecond pulses are suitable for manipulation of the initial steps in laser processing of high band gap materials.

Photoelectron Circular Dichroism of Bicyclic Ketones from Multiphoton Ionization with Femtosecond Laser Pulses

Photoelectron circular dichroism (PECD) is a CD effect up to the ten-percent regime and shows contributions from higher-order Legendre polynomials when multiphoton ionization is compared to single-photon ionization. We give a full account of our experimental methodology for measuring the multiphoton PECD and derive quantitative measures that we apply on camphor, fenchone and norcamphor. Different modulations and amplitudes of the contributing Legendre polynomials are observed despite the similarity in chemical structure. In addition, we study PECD for elliptically polarized light employing tomographic reconstruction methods. Intensity studies reveal dissociative ionization as the origin of the observed PECD effect, whereas ionization of the intermediate resonance is dominating the signal. As a perspective, we suggest to make use of our tomographic data as an experimental basis for a complete photoionization experiment and give a prospect of PECD as an analytic tool.

Nanofabrication of tailored surface structures in dielectrics using temporally shaped femtosecond-laser pulses

We have investigated the use of tightly focused, temporally shaped femtosecond (fs)-laser pulses for producing nanostructures in two dielectric materials (sapphire and phosphate glass) with different characteristics in their response to pulsed laser radiation. For this purpose, laser pulses shaped by third-order dispersion (TOD) were used to generate temporally asymmetric excitation pulses, leading to the single-step production of subwavelength ablative and subablative surface structures. When compared to previous works on the interaction of tightly focused TOD-shaped pulses with fused silica, we show here that this approach leads to very different nanostructure morphologies, namely, clean nanopits without debris surrounding the crater in sapphire and well-outlined nanobumps and nanovolcanoes in phosphate glass. Although in sapphire the debris-free processing is associated with the much lower viscosity of the melt compared to fused silica, nanobump formation in phosphate glass is caused by material network expansion (swelling) upon resolidification below the ablation threshold. The formation of nanovolcanoes is a consequence of the combined effect of material network expansion and ablation occurring in the periphery and central part of the irradiated region, respectively. It is shown that the induced morphologies can be efficiently controlled by modulating the TOD coefficient of the temporally shaped pulses.

Morphology of nanoscale structures on fused silica surfaces from interaction with temporally tailored femtosecond pulses

Laser control of two basic ionization processes on fused silica, i.e., multiphoton ionization and avalanche ionization, with temporally asymmetric pulse envelopes is investigated. Control leads to different final electron densities/energies as the direct temporal intensity profile and the time inverted intensity profile address the two ionization processes in a different fashion. This results in observed different thresholds for material modification on the surface as well as in reproducible lateral structures being an order of magnitude below the diffraction limit (down and below 100 nm at a numerical aperture of 0.5). In this contribution, the morphology of the resulting structures is discussed.

Enantiomeric Excess Sensitivity to Below One Percent by Using Femtosecond Photoelectron Circular Dichroism

Photoelectron circular dichroism (PECD) is experimentally investigated with chiral specimens with varying amounts of enantiomeric excess (ee). As a prototype, we measure and analyze the photoelectron angular distribution from randomly oriented fenchone molecules in the gas phase that result from ionization with circularly polarized femtosecond laser pulses. The quantification of these measurements shows a linear dependence with respect to the ee values. In addition, differences in the ee values (denoted as detection limit) of below one percent can be distinguished for nearly enantiopure samples, as well as for almost racemates. In combination with the use of a reference, the assignment of absolute ee values is possible. The present measurement time is a few minutes, but this could be reduced. This table-top laser-based approach should facilitate widespread implementation in chiral analysis.

Temporal Airy pulses for controlled high aspect ratio nanomachining of dielectrics

Understanding the interplay between optical pulse parameters and ultrafast material response is critical in achieving efficient and controlled laser nanomachining. In general, the key to initiate material processing is the deposition of a sufficient energy density within the electronic system. In dielectrics this critical energy density corresponds typically to a plasma frequency in the near-IR spectral region. Creating this density instantaneously with ultrashort laser pulses of a few tens of femtoseconds pulse duration in the same spectral region, the penetration depth into the material will strongly decrease with increasing electron density. Consequently, staying below this critical density will allow deep penetration depths. This calls for delayed ionization processes to deposit the energy for processing, thus introducing the temporal structure of the laser pulses as a control parameter. In this contribution we demonstrate this concept experimentally and substantiate the physical picture with numerical calculations. Bandwidth-limited pulses of 30 fs pulse duration are stretched up to 1.5 ps either temporally symmetrically or temporally asymmetrically. The interplay between pulse structure and material response is optimally exploited by the asymmetrically structured temporal Airy pulses leading to the inherently efficient creation of high aspect ratio nanochannels. Depths in the range of several micrometers and diameters around 250 nm are created within a single laser shot and without making use of self-focusing and filamentation processes. In addition to the machining of nanophotonic devices in dielectrics, the technique has the potential to enhance laser-based nanocell surgery and cell poration techniques.

Coupled electron-nuclear wavepacket dynamics in potassium dimers

Recently we have demonstrated control of valence-bond excitation of a molecule due to the interplay of the induced charge oscillation with the precisely tailored phase of the driving laser field (Bayer et al 2013 Phys. Rev. Lett. 110 123003). In this contribution we describe in more detail the two-colour experiment—a control pulse sequence followed by an ionizing probe pulse of a different wavelength. We provide details on the quantum dynamics simulations carried out to reproduce and to analyse the experimental results. The procedure for averaging over the focal intensity distribution in the interaction region and the method for orientation averaging, which are both crucial for the reproduction of our strong-field measurements, are also described in detail. The analysis of the temporal evolution of the expectation values of the wavepackets on the relevant potentials, the induced energetic shifts in the molecule and the modulation in the charge oscillation provides further insights into the interplay of the coupled nuclear-electron dynamics. Because the measured photoelectron spectra reveal the population of the target states we describe the quantum mechanical approach to calculate the photoelectron spectra and rationalize the results using Mullikens difference potential method.