Laser-Pulse-Length Effects in Ultrafast Laser Desorption.

Shortening the laser pulse length opens up new opportunities for laser desorption (LD) of molecules, with benefits for mass spectrometry (MS) sampling and ionization. The capability to ablate any material without the need for an absorbing matrix and the decrease of thermal damage and molecular fragmentation has promoted various applications with very different parameters and postionization techniques. However, the key issues of the optimum laser pulse length and intensity to achieve efficient and gentle desorption of molecules for postionization in MS are not resolved, although these parameters determine the costs and complexity of the required laser system. Here, we address this research gap with a systematic study on the effect of the pulse length on the LD of molecules. Keeping all other optical and ionization parameters constant, we directly compared the pulses in the femtosecond, picosecond, and nanosecond range with respect to LD-induced fragmentation and desorption efficiency. To represent real-world applications, we investigated the LD of over-the-counter medicaments naproxen and ibuprofen directly from tablets as well as the LD of retene and ship emission aerosols from a quartz filter. With our study design, we excluded interfering effects on fragmentation and LD efficiency from, for example, collisional cooling or postionization by performing the experiments in vacuum with resonance-enhanced multiphoton ionization as the postionization technique. Regarding LD-induced fragmentation, we already found benefits for the picosecond pulses. However, the efficiency of LD was found to continuously increase with decreasing pulse length, pointing to the application potential of ultrashort pulses in trace analytics. Because many interfering effects beyond the LD pulse length could be excluded in the experiment, our results may be directly transferable to the LD applied in other techniques.

Three-dimensional femtosecond snapshots of isolated faceted nanostructures.

The structure and dynamics of isolated nanosamples in free flight can be directly visualized via single-shot coherent diffractive imaging using the intense and short pulses of x-ray free-electron lasers. Wide-angle scattering images encode three-dimensional (3D) morphological information of the samples, but its retrieval remains a challenge. Up to now, effective 3D morphology reconstructions from single shots were only achieved via fitting with highly constrained models, requiring a priori knowledge about possible geometries. Here, we present a much more generic imaging approach. Relying on a model that allows for any sample morphology described by a convex polyhedron, we reconstruct wide-angle diffraction patterns from individual silver nanoparticles. In addition to known structural motives with high symmetries, we retrieve imperfect shapes and agglomerates that were not previously accessible. Our results open unexplored routes toward true 3D structure determination of single nanoparticles and, ultimately, 3D movies of ultrafast nanoscale dynamics.

Vacuum Laser Photoionization inside the C-trap of an Orbitrap Mass Spectrometer: Resonance-Enhanced Multiphoton Ionization High-Resolution Mass Spectrometry.

State-of-the-art mass spectrometry with ultraviolet (UV) photoionization is mostly limited to time-of-flight (ToF) mass spectrometers with 1000-10 000 m/Δm mass resolution. However, higher resolution and higher spectral dynamic range mass spectrometry may be indispensable in complex mixture characterization. Here, we present the concept, implementation, and initial evaluation of a compact ultrahigh-resolution mass spectrometer with gas-phase laser ionization. The concept is based on direct laser photoionization in the ion accumulation and ejection trap (C-trap) of an Orbitrap mass spectrometer. Resonance-enhanced multiphoton ionization (REMPI) using 266 nm UV pulses from a frequency-quadrupled Nd:YAG laser was applied for selective and efficient ionization of monocyclic and polycyclic aromatic hydrocarbons. The system is equipped with a gas inlet for volatile compounds and a heated gas chromatography coupling. The former can be employed for rapid system m/z-calibration and performance evaluation, whereas the latter enables analysis of semivolatile and higher-molecular-weight compounds. The capability to evaluate complex mixtures is demonstrated for selected petrochemical materials. In these experiments, several hundred to over a thousand compounds could be attributed with a root-mean-square mass error generally below 1 ppm and a mass resolution of over 140 000 at 200 m/z. Isobaric interferences could be resolved, and narrow mass splits, such as 3.4 mDa (SH4/C3), are determined. Single laser shots provided limits of detection in the 20-ppb range for p-xylene and 1,2,4-trimethylbenzene, similar to compact vacuum REMPI-ToF systems.

Spatially Shaped Laser Pulses for the Simultaneous Detection of Polycyclic Aromatic Hydrocarbons as well as Positive and Negative Inorganic Ions in Single Particle Mass Spectrometry.

Polycyclic aromatic hydrocarbons (PAHs) are toxic organic trace components in atmospheric aerosols that have impacts on climate and human health. They are bound to airborne particles and transported over long distances. Observations of their distribution, transport pathways, and degradation are crucial for risk assessment and mitigation. Such estimates would benefit from online detection of PAHs along with analysis of the carrying particles to identify the source. Typically, laser desorption/ionization (LDI) in a bipolar mass spectrometer reveals the inorganic constituents and provides limited molecular information. In contrast, two-step ionization approaches produce detailed PAH mass spectra from individual particles but without the source-specific inorganic composition. Here we report a new technique that yields the single-particle PAH composition along with both positive and negative inorganic ions via LDI. Thus, the complete particle characterization and source apportionment from conventional bipolar LDI-analysis becomes possible, combined with a detailed PAH spectrum for the same particle. The key idea of the method is spatiotemporal matching of the ionization laser pulse to the transient component distribution in the particle plume after laser desorption. The technique is robust and field-deployable with only slightly higher costs and complexity compared to two-step approaches. We demonstrate its capability to reveal the PAH-distribution on different particle types in combustion aerosols and ambient air.

Publisher Correction: Nanoplasmonic electron acceleration by attosecond-controlled forward rescattering in silver clusters.

The original PDF version of this Article contained an error in Equation 1. The original HTML version of this Article contained errors in Equation 2 and Equation 4. These errors have now been corrected in both the PDF and the HTML versions of the Article.

Nanoplasmonic electron acceleration by attosecond-controlled forward rescattering in silver clusters.

In the strong-field photoemission from atoms, molecules, and surfaces, the fastest electrons emerge from tunneling and subsequent field-driven recollision, followed by elastic backscattering. This rescattering picture is central to attosecond science and enables control of the electron's trajectory via the sub-cycle evolution of the laser electric field. Here we reveal a so far unexplored route for waveform-controlled electron acceleration emerging from forward rescattering in resonant plasmonic systems. We studied plasmon-enhanced photoemission from silver clusters and found that the directional acceleration can be controlled up to high kinetic energy with the relative phase of a two-color laser field. Our analysis reveals that the cluster's plasmonic near-field establishes a sub-cycle directional gate that enables the selective acceleration. The identified generic mechanism offers robust attosecond control of the electron acceleration at plasmonic nanostructures, opening perspectives for laser-based sources of attosecond electron pulses.

Formation of coherent rotational wavepackets in small molecule-helium clusters using impulsive alignment.

We show that rotational line spectra of molecular clusters with near zero permanent dipole moments can be observed using impulsive alignment. Aligned rotational wavepackets were generated by non-resonant interaction with intense femtosecond laser pump pulses and then probed using Coulomb explosion by a second, time-delayed femtosecond laser pulse. By means of a Fourier transform a rich spectrum of rotational eigenstates was derived. For the smallest cluster, C(2)H(2)-He, we were able to establish essentially all rotational eigenstates up to the dissociation threshold on the basis of theoretical level predictions. The C(2)H(2)-He complex is found to exhibit distinct features of large amplitude motion and very early onset of free internal rotor energy level structure.