Bloch k-selective resonant inelastic scattering of hard X-rays from valence electrons of 3d-metals

Die Form von resonant angeregen Valenz-Fluoreszenzspektren hängt sowohl vonder Energie der einfallenden Strahlung, als auch von Größe und Richtung desImpulsübertrags q ab, falls harte Röntgenstrahlen benutzt werden. DieserEffekt ist auf die elektronische Bandstruktur der Valenz- undLeitungselektronen der Probe, in Kombination mit der Energie- undImpulserhaltung des Streuprozesses zurückzuführen, woraus dieBloch-k-Impulserhaltung des resonant inelastischen Streuprozesses folgt.In dieser Arbeit wird die Gültigkeit der Bloch-k-Impulserhaltung im Bereichder harten Röntgenstrahlen und ihre Anwendbarkeit auf metallische Probengezeigt. Dazu werden die K-Kante von Cu und die K-Kante von Ni in NiAluntersucht. Ausgehend von einer LAPW Bandstrukturrechnung werden resonantangerege Valenz-Fluoreszensspektren berechnet. Diese stimmen gut mit dengemessenen Spektren überein.Weiterhin werden mehrere Effekte untersucht, die den Bloch-k-erhaltendenresonant inelasischen Röntgenstreuprozess beeinflussen.Im Gegensatz zur Streuung im Bereich der weichen Röntgenstrahlung ist an derK-Kante von Cu keine Zerstörung der Bloch-k-Erhaltung durchElektron-Phonon-Wechselwirkung im Zwischenzustand meßbar. In der Tat ist nurein kleiner nicht-k-erhaltender Anteil von wenigen Prozent zu erwarten, dadie Lebensdauer des 1s Rumpf-Lochs von Cu kürzer als dieElektron-Phonon-Wechselwirkungszeit ist.Mit Hilfe einer Superzellen-Rechnung an Cu wird gezeigt, daß die Abschirmungdes 1s-Rumpf-Lochs keinen Einfluß auf den Streuprozeß hat, falls an denK-Kanten der schweren 3d-Übergangsmetalle angeregt wird. DieSuperzellen-Methode wird im Detail beschrieben, und die Konvergenz derLadungsdichte bezüglich der Größe der Superzelle wird ausführlichuntersucht.Die Intensität des 3d-nach-1s-Quadupolübergangs relativ zum4p-nach-1s-Dipolübergang wird durch die Berechnung der entsprechendenÜbergangs-Matrixelemente bestimmt. Das Ergebnis wird anhand von Ga, Ge undAs überprüft, indem berechnete Floreszenzspektren mit gemessenen verglichenwerden, da für diese Elemente die 3d-Fluoreszenzlinie von der4p-Fluoreszenzlinie getrennt ist. Ferner wird die Abschirmung des3d9-Endzustands im Fall des 3d-nach-1s-Quadrupolübergangs untersucht. Damitist es möglich, sowohl die Intensität als auch die energetische Position desQuadrupolbeitrags zur Fluoreszenz für Cu zu bestimmen.Die Valenz-Fluoreszenzlinie der schweren 3d-Übergangsmetalle wird teilweisevom radiativen KNN Auger-Satelliten ueberdeckt. Die Intensität diesesSatelliten, dem ein Doppelionisationsprozess während der Emission einesFluoreszenzphotons zugrunde liegt, wird für die Elemente Co bis Asuntersucht. Um die Satellitenlinie in der Auswertung von Bloch-k-selektivenValenz-Fluoreszenzspektren richtig berücksichtigen zu können, wird derKNN-Satellit im Rahmen eines semiempirischen Modells behandelt, das aus demresonant inelastischen Streuquerschnitt hergeleitet und anhand derradiativen KMN- und KMM-Auger-Satelliten von Cu bestätigt wird Darüber hinaus werden die Cu K beta' und Cu K beta'' Satelliten der Cu Kbeta_1,3 Fluoreszenzlinie untersucht. Diese Satelliten stammen von einemDoppelionisationsprozeß während der Absorption eines Photons. Aus ihrerSchwellenenergie kann geschlossen werden, daß ihnen ein3d-Zuschauer-Lochzustand zugrunde liegt, während der kurze Sättigungsbereichdarauf hindeutet, daß diese Satelliten von shakeup-Prozessen dominiertwerden.The shape of resonantly excited valence fluorescence spectra depends on theenergy of the incident radiation as well as on the size and the direction ofthe momentum transfer q if hard x-rays are used. This effect is due to theelectronic band structure of the valence and conduction electrons of thesample in combination with the energy and momentum conservation of thescattering process, giving rise to the law of Bloch k-momentum conservationof the resonant inelastic scattering process.In this thesis, the validity of the Bloch k-momentum conservation in thehard x-ray regime and its applicability to metallic samples are demonstratedby probing the K edge of Cu and the K edge of Ni in NiAl. Based on a LAPWbandstructure calculation resonantly excited valence fluorescence spectraare calculated. These agree well with the measured spectra.Four effects influencing the Bloch k-conserving resonant inelastic x-rayscattering process have been investigated. In contrast to scattering in the soft x-ray regime a destruction of thek-conservation due to electron-phonon interaction in the intermediate stateis not measurable at the K edge of Cu. Indeed, only a small k-unselectivefraction of a few percent is expected, since the lifetime of the 1s corehole in Cu is shorter than the electron-phonon interaction time.By means of a supercell calculation of Cu it is found that screening of the1s core hole does not alter the scattering process if the K edges of thelate 3d elements are probed. A detailed description of the supercellapproach is given. The convergence of the charge density with respect to thesize of the supercell is thoroughly investigated.The intensity of the quadrupolar 3d-to-1s transition relative to the dipolar4p-to-1s transition is obtained from the calculation of the correspondingtransition matrix elements. The result is verified by comparing calculatedto measured fluorescence spectra in the case of Ga, Ge, and As, where the 3dfluorescence line is separated from the 4p fluorescence line. Moreover, thescreening of the 3d9 final state configuration in case of the quadrupolar3d-to-1s transition is investigated. This allows to determine properly theintensity and the energetic position of the quadrupolar fluorescencecontribution in the case of Cu.The valence fluorescence lines of the late 3d elements is partly obscured bythe KNN radiative Auger satellite. The intensity of this satellite line,which is due to a double ionization process during the emission of afluorescence photon, is investigated for the elements from Co to As. Inorder to be properly considered in the interpretation of the Blochk-selective valence floresence spectra, the shape of the KNN satellite isaccounted for by a semiempirical model, which is derived from the resonantinelastic scattering cross section. The model is confirmed by investigatingthe KMN and KMM radiative Auger satellites of Cu.Moreover, the Cu K beta' and Cu K beta'' satellites of the Cu K beta_1,3fluorescence line are examined. These satellites stem from a doubleionization process during the absorption of a photon. From their thresholdenergy it is possible to confirm that they are due to a 3d spectator hole.The short saturation range indicates that these satellites are dominated byshakeup processes

Magnetic circular dichroism in X-ray fluorescence of Heusler alloys at threshold excitation

The results of fluorescence measurements of magnetic circular dichroism (MCD) in Mn L_2,L_3 X-ray emission and absorption for Heusler alloys NiMnSb and Co2MnSb are presented. Very intense resonance Mn L_3 emission is found at the Mn 2p_3/2 threshold and is attributed to a peculiarity of the threshold excitation in materials with the half-metallic character of the electronic structure. A theoretical model for the description of resonance scattering of polarized x-rays is suggested.Comment: 3 pages, 2 figures. Discussed at conferences, submitting process in progres

A regio- and stereoselective ω-transaminase/monoamine oxidase cascade for the synthesis of chiral 2,5-disubstituted pyrrolidines

Biocatalytic approaches to the synthesis of optically pure chiral amines, starting from simple achiral building blocks, are highly desirable because such motifs are present in a wide variety of important natural products and pharmaceutical compounds. Herein, a novel one-pot ω-transaminase (TA)/monoamine oxidase (MAO-N) cascade process for the synthesis of chiral 2,5-disubstituted pyrrolidines is reported. The reactions proceeded with excellent enantio- and diastereoselectivity (>94 % ee; >98 % de) and can be performed on a preparative scale. This methodology exploits the complementary regio- and stereoselectivity displayed by both enzymes, which ensures that the stereogenic center established by the transaminase is not affected by the monoamine oxidase, and highlights the potential of this multienzyme cascade for the efficient synthesis of chiral building blocks

Damage accumulation in thin ruthenium films induced by repetitive exposure to femtosecond XUV pulses below the single shot ablation threshold

The process of damage accumulation in thin ruthenium films exposed to multiple femtosecond XUV free electron laser FEL pulses below the critical angle of reflectance at the Free electron LASer facility in Hamburg FLASH was experimentally analyzed. The multi shot damage threshold is found to be lower than single shot damage threshold. Detailed analysis of the damage morphology and its dependence on irradiation conditions justifies the assumption that cavitation induced by the FEL pulse is the prime mechanism responsible for multi shot damage in optical coating

Characterization of megahertz X ray laser beams by multishot desorption imprints in PMMA

Proper diagnostics of intense free electron laser FEL X ray pulses is indisputably important for experimental data analysis as well as for the protection of beamline optical elements. New challenges for beam diagnostic methods are introduced by modern FEL facilities capable of delivering powerful pulses at megahertz MHz repetition rates. In this paper, we report the first characterization of a defocused MHz 13.5 nm beam generated by the free electron laser in Hamburg FLASH using the method of multi pulse desorption imprints in poly methyl methacrylate PMMA . The beam fluence profile is reconstructed in a novel and highly accurate way that takes into account the nonlinear response of material removal to total dose delivered by multiple pulses. The algorithm is applied to experimental data of single shot ablation imprints and multi shot desorption imprints at both low 10 Hz and high 1 MHz repetition rates. Reconstructed response functions show a great agreement with the theoretical desorption response function mode

Mechanism of single shot damage of Ru thin films irradiated by femtosecond extreme UV free electron laser

Ruthenium is a perspective material to be used for XUV mirrors at free electron laser facilities. Yet, it is still poorly studied in the context of ultrafast laser matter interaction. In this work, we present single shot damage studies of thin Ru films irradiated by femtosecond XUV free electron laser pulses at FLASH. Ex situ analysis of the damaged spots, performed by different types of microscopy, shows that the weakest detected damage is surface roughening. For higher fluences we observe ablation of Ru. Combined simulations using Monte Carlo code XCASCADE 3D and the two temperature model reveal that the damage mechanism is photomechanical spallation, similar to the case of irradiating the target with optical lasers. The analogy with the optical damage studies enables us to explain the observed damage morphologie

Experimental study of EUV mirror radiation damage resistance under long term free electron laser exposures below the single shot damage threshold

The durability of grazing and normal incidence optical coatings has been experimentally assessed under free electron laser irradiation at various numbers of pulses up to 16 million shots and various fluence levels below 10 of the single shot damage threshold. The experiment was performed at FLASH, the Free electron LASer in Hamburg, using 13.5 nm extreme UV EUV radiation with 100 fs pulse duration. Polycrystalline ruthenium and amorphous carbon 50 nm thin films on silicon substrates were tested at total external reflection angles of 20 and 10 grazing incidence, respectively. Mo Si periodical multilayer structures were tested in the Bragg reflection condition at 16 off normal angle of incidence. The exposed areas were analysed post mortem using differential contrast visible light microscopy, EUV reflectivity mapping and scanning X ray photoelectron spectroscopy. The analysis revealed that Ru and Mo Si coatings exposed to the highest dose and fluence level show a few per cent drop in their EUV reflectivity, which is explained by EUV induced oxidation of the surfac

Role of heat accumulation in the multi-shot damage of silicon irradiated with femtosecond XUV pulses at a 1 MHz repetition rate

The role played by heat accumulation in multi-shot damage of silicon was studied. Bulk silicon samples were exposed to intense XUV monochromatic radiation of a 13.5 nm wavelength in a series of 400 femtosecond pulses, repeated with a 1 MHz rate (pulse trains) at the FLASH facility in Hamburg. The observed surface morphological and structural modifications are formed as a result of sample surface melting. Modifications are threshold dependent on the mean fluence of the incident pulse train, with all threshold values in the range of approximately 36-40 mJ/cm². Experimental data is supported by a theoretical model described by the heat diffusion equation. The threshold for reaching the melting temperature (45 mJ/cm²) and liquid state (54 mJ/cm²), estimated from this model, is in accordance with experimental values within measurement error. The model indicates a significant role of heat accumulation in surface modification processes