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- ItemIR-MALDI Mass Spectrometry Imaging with Plasma Post-Ionization of Nonpolar Metabolites(Columbus, Ohio : American Chemical Society, 2022) Schneemann, Julian; Schäfer, Karl-Christian; Spengler, Bernhard; Heiles, SvenAmbient mass spectrometry imaging (MSI) methods come with the advantage of visualizing biomolecules from tissues with no or minimal sample preparation and operation under atmospheric-pressure conditions. Similar to all other MSI methodologies, however, ambient MSI modalities suffer from a pronounced bias toward either polar or nonpolar analytes due to the underlying desorption and ionization mechanisms of the ion source. In this study, we present the design, construction, testing, and application of an in-capillary dielectric barrier discharge (DBD) module for post-ionization of neutrals desorbed by an ambient infrared matrix-assisted laser desorption/ionization (IR-MALDI) MSI source. We demonstrate that the DBD device enhances signal intensities of nonpolar compounds by up to 104 compared to IR-MALDI without affecting transmission of IR-MALDI ions. This allows performing MSI experiments of mouse tissue and Danaus plexippus caterpillar tissue sections, visualizing the distribution of sterols, fatty acids, monoglycerides, and diglycerides that are not detected in IR-MALDI MSI experiments. The pronounced signal enhancement due to IR-MALDI-DBD compared to IR-MALDI MSI enables mapping of nonpolar analytes with pixel resolutions down to 20 μm in mouse brain tissue and to discern the spatial distribution of sterol lipids characteristic for histological regions of D. plexippus.
- ItemInteratomic and Intermolecular Coulombic Decay(Washington, DC : ACS Publ., 2020) Jahnke, Till; Hergenhahn, Uwe; Winter, Bernd; Dörner, Reinhard; Frühling, Ulrike; Demekhin, Philipp V.; Gokhberg, Kirill; Cederbaum, Lorenz S.; Ehresmann, Arno; Knie, André; Dreuw, AndreasInteratomic or intermolecular Coulombic decay (ICD) is a nonlocal electronic decay mechanism occurring in weakly bound matter. In an ICD process, energy released by electronic relaxation of an excited atom or molecule leads to ionization of a neighboring one via Coulombic electron interactions. ICD has been predicted theoretically in the mid nineties of the last century, and its existence has been confirmed experimentally approximately ten years later. Since then, a number of fundamental and applied aspects have been studied in this quickly growing field of research. This review provides an introduction to ICD and draws the connection to related energy transfer and ionization processes. The theoretical approaches for the description of ICD as well as the experimental techniques developed and employed for its investigation are described. The existing body of literature on experimental and theoretical studies of ICD processes in different atomic and molecular systems is reviewed. © 2020 American Chemical Society
- ItemExcited-state relaxation of hydrated thymine and thymidine measured by liquid-jet photoelectron spectroscopy: experiment and simulation(Washington, DC : ACS Publications, 2015) Buchner, Franziska; Nakayama, Akira; Yamazaki, Shohei; Ritze, Hans-Hermann; Lübcke, AndreaTime-resolved photoelectron spectroscopy is performed on thymine and thymidine in aqueous solution to study the excited-state relaxation dynamics of these molecules. We find two contributions with sub-ps lifetimes in line with recent excited-state QM/MM molecular dynamics simulations (J. Chem. Phys.2013, 139, 214304). The temporal evolution of ionization energies for the excited ππ* state along the QM/MM molecular dynamics trajectories were calculated and are compatible with experimental results, where the two contributions correspond to the relaxation paths in the ππ* state involving different conical intersections with the ground state. Theoretical calculations also show that ionization from the nπ* state is possible at the given photon energies, but we have not found any experimental indication for signal from the nπ* state. In contrast to currently accepted relaxation mechanisms, we suggest that the nπ* state is not involved in the relaxation process of thymine in aqueous solution.
- ItemIntracycle interference in ionization of Ar by a laser assisted XUV pulse(Bristol : IOP Publ., 2017) Arbó, D.G.; López, S. D.; Kubin, M.; Hummert, J.; Vrakking, M.J.J.; Kornilov, O.Synopsis We present a theoretical and experimental study of the subcycle interference in laser assisted XUV ionization of Ar atoms. Averaging over the focal volume happens to blur the intracycle interference, which thus cannot be measured directly. We show that even at these conditions, the intracycle interference can be obtained through the subtraction of two different angle and energy-resolved distributions at slightly different laser intensities.
- ItemPhotoelectron holography in strong optical and dc electric fields(Bristol : Institute of Physics Publishing, 2014) Stodolna, A.; Huismans, Y.; Rouzée, A.; Lépine, F.; Vrakking, M.J.J.The application of velocity map imaging for the detection of photoelectrons resulting from atomic or molecular ionization allows the observation of interferometric, and in some cases holographic structures that contain detailed information on the target from which the photoelecrons are extracted. In this contribution we present three recent examples of the use of photoelectron velocity map imaging in experiments where atoms are exposed to strong optical and dc electric fields. We discuss (i) observations of the nodal structure of Stark states of hydrogen measured in a dc electric field, (ii) mid-infrared strong-field ionization of metastable Xe atoms and (iii) the reconstruction of helium electronic wavepackets in an attosecond pump-probe experiment. In each case, the interference between direct and indirect electron pathways, reminiscent of the reference and signal waves in holography, is seen to play an important role.
- ItemAbove-threshold ionization in a bicircular field: Quantum orbits unfolding in a plane(Bristol : IOP Publ., 2017) Becker, W.; Milošević, D.B.Above-threshold ionization (ATI) of atoms by a strong bicircular laser field is investigated using the strong-field approximation and the quantum-orbit theory. The bicircular field consists of two coplanar counterrotating circularly polarized fields with a frequency ratio of 2:1. The velocity map of the angle-resolved ATI spectra, both for direct and rescattered electrons, reflects the shape of a parametric plot of the bicircular field and its symmetries. It is shown that the main characteristics of the ATI spectra can be explained using only a few quantum orbits having short travel times. We also analyze a recently discovered [Phys. Rev. A 93, 052402(R) (2016)] bicircular-field-induced spin asymmetry of the ATI electrons and show that the momentum dependence of the spin-asymmetry parameter is stronger for longer wavelengths.
- ItemIntracluster Coulombic decay following intense NIR ionization of clusters(Bristol : IOP Publ., 2015) Schütte, Bernd; Arbeiter, Mathias; Fennel, Thomas; Jabbari, Ghazal; Gokhberg, Kirill; Kuleff, Alexander I.; Vrakking, Marc J. J.; Rouzée, ArnaudWe report on the observation of a novel intracluster Coulombic decay process following Rydberg atom formation in clusters ionized by intense near-infrared fields. A new decay channel emerges, in which a Rydberg atom relaxes to the ground state by transferring its excess energy to a weakly bound electron in the environment that is emitted from the cluster. We find evidence for this process in the electron spectra, where a peak close to the corresponding atomic ionization potential is observed. For Ar clusters, a decay time of 87 ps is measured, which is significantly longer than in previous time-resolved studies of interatomic Coulombic decay.
- ItemAttosecond control of electron-ion recollision in high harmonic generation(Bristol : IOP, 2011) Gademann, G.; Kelkensberg, F.; Siu, W.K.; Johnsson, P.; Gaarde, M.B.; Schafer, K.J.; Vrakking, M.J.J.We show that high harmonic generation driven by an intense nearinfrared (IR) laser can be temporally controlled when an attosecond pulse train (APT) is used to ionize the generation medium, thereby replacing tunnel ionization as the first step in the well-known three-step model. New harmonics are formed when the ionization occurs at a well-defined time within the optical cycle of the IR field. The use of APT-created electron wave packets affords new avenues for the study and application of harmonic generation. In the present experiment, this makes it possible to study harmonic generation at IR intensities where tunnel ionization does not give a measurable signal.
- ItemInterference structure of above-threshold ionization versus above-threshold detachment(Bristol : IOP, 2012) Korneev, Ph.A.; Popruzhenko, S.V.; Goreslavski, S.P.; Becker, W.; Paulus, G.G.; Fetić, B.; Milošević, D.B.Laser-induced electron detachment or ionization of atoms and negative ions is considered. In the context of the saddle-point evaluation of the strong-field approximation (SFA), the velocity maps of the direct electrons (those that do not undergo rescattering) exhibit a characteristic structure due to the constructive and destructive interference of electrons liberated from their parent atoms/ions within certain windows of time. This structure is defined by the above-threshold ionization rings at fixed electron energy and by two sets of curves in momentum space on which destructive interference occurs. The spectra obtained with the SFA are compared with those obtained by numerical solution of the time-dependent Schrödinger equation. For detachment, the agreement is excellent. For ionization, the effect of the Coulomb field is most pronounced for electrons emitted in a direction close to laser polarization, while for nearperpendicular emission the qualitative appearance of the spectrum is unaffected.
- ItemUnified description of low-order above-threshold ionization on and off axis(Bristol : IOP Publ., 2016) Becker, W.; Milošević, D.B.A recently developed unified description of low-order above-threshold ionization (Becker et al 2014 J. Phys. B: At. Mol. Opt. Phys. 47 204022; 2015 J. Phys. B: At. Mol. Opt. Phys. 48 151001) is revisited and extended. By considering the rescattering electron energies and angles at the classical cutoffs and the contributions of particular quantum-orbit solutions, it is shown that summing both the backward- and the forward-scattering contributions, within the low-frequency approximation, it is possible to reproduce the observed features of the ATI spectra both for low and high energies and both on and off the laser-polarization axis in the momentum plane.