RESUMO
Coherent control of quantum dynamics is key to a multitude of fundamental studies and applications1. In the visible or longer-wavelength domains, near-resonant light fields have become the primary tool with which to control electron dynamics2. Recently, coherent control in the extreme-ultraviolet range was demonstrated3, with a few-attosecond temporal resolution of the phase control. At hard-X-ray energies (above 5-10 kiloelectronvolts), Mössbauer nuclei feature narrow nuclear resonances due to their recoilless absorption and emission of light, and spectroscopy of these resonances is widely used to study the magnetic, structural and dynamical properties of matter4,5. It has been shown that the power and scope of Mössbauer spectroscopy can be greatly improved using various control techniques6-16. However, coherent control of atomic nuclei using suitably shaped near-resonant X-ray fields remains an open challenge. Here we demonstrate such control, and use the tunable phase between two X-ray pulses to switch the nuclear exciton dynamics between coherent enhanced excitation and coherent enhanced emission. We present a method of shaping single pulses delivered by state-of-the-art X-ray facilities into tunable double pulses, and demonstrate a temporal stability of the phase control on the few-zeptosecond timescale. Our results unlock coherent optical control for nuclei, and pave the way for nuclear Ramsey spectroscopy17 and spin-echo-like techniques, which should not only advance nuclear quantum optics18, but also help to realize X-ray clocks and frequency standards19. In the long term, we envision time-resolved studies of nuclear out-of-equilibrium dynamics, which is a long-standing challenge in Mössbauer science20.
RESUMO
TEMPUS is a new detector system being developed for photon science. It is based on the Timepix4 chip and, thus, it can be operated in two distinct modes: a photon-counting mode, which allows for conventional full-frame readout at rates up to 40â kfps; and an event-driven time-stamping mode, which allows excellent time resolution in the nanosecond regime in measurements with moderate X-ray flux. In this paper, the initial prototype, a single-chip device, is introduced, and the readout system described. Moreover, and in order to evaluate its capabilities, some tests were performed at PETRAâ III and ESRF for which results are also presented.
RESUMO
Using the density functional theory, we study the structural and lattice dynamical properties of europium sesquioxide (Eu2O3) in the cubic, trigonal, and monoclinic phases. The obtained lattice parameters and energies of the Raman modes show a good agreement with the available experimental data. The Eu-partial phonon density of states calculated for the cubic structure is compared with the nuclear inelastic scattering data obtained from a 20 nm thick Eu2O3 film deposited on a YSZ substrate. A small shift of the experimental spectrum to higher energies results from a compressive strain induced by the substrate. On the basis of lattice and phonon properties, we analyze the mechanisms of structural transitions between different phases of Eu2O3.
RESUMO
The spin crossover (SCO) efficiency of [57Fe(bpz)2(phen)] (where bpz = bis(pyrazol-1-yl)borohydride and phen = 9,10-phenantroline) molecules deposited on gold substrates was investigated by means of synchrotron Mössbauer spectroscopy. The spin transition was driven thermally, or light induced via the LIESST (light induced excited spin-state trapping) effect. Both sets of measurements show that, once deposited on a gold substrate, the efficiency of the SCO mechanism is modified with respect to molecules in the bulk phase. A correlation in the distribution of hyperfine parameters in the sublimated films, not evidenced so far in the bulk phase, is reported. This translates into geometrical distortions of the first coordination sphere of the iron atom that seem to correlate with the decreased spin conversion. The work reported clearly shows the potentiality of synchrotron Mössbauer spectroscopy for the characterization of nanostructured Fe-based SCO systems, thus resulting as a key tool in view of their applications in innovative nanoscale devices.
RESUMO
α-Sb2O3 (senarmontite), ß-Sb2O3 (valentinite), and α-TeO2 (paratellurite) are compounds with pronounced stereochemically active Sb and Te lone pairs. The vibrational and lattice properties of each have been previously studied but often lead to incomplete or unreliable results due to modes being inactive in infrared or Raman spectroscopy. Here, we present a study of the relationship between bonding and lattice dynamics of these compounds. Mössbauer spectroscopy is used to study the structure of Sb in α-Sb2O3 and ß-Sb2O3, whereas the vibrational modes of Sb and Te for each oxide are investigated using nuclear inelastic scattering, and further information on O vibrational modes is obtained using inelastic neutron scattering. Additionally, vibrational frequencies obtained by density functional theory (DFT) calculations are compared with experimental results in order to assess the validity of the utilized functional. Good agreement was found between DFT-calculated and experimental density of phonon states with a 7% scaling factor. The Sb-O-Sb wagging mode of α-Sb2O3 whose frequency was not clear in most previous studies is experimentally observed for the first time at â¼340 cm-1. Softer lattice vibrational modes occur in orthorhombic ß-Sb2O3 compared to cubic α-Sb2O3, indicating that the antimony bonds are weakened upon transforming from the molecular α phase to the layer-chained ß structure. The resulting vibrational entropy increase of 0.45 ± 0.1 kB/Sb2O3 at 880 K accounts for about half of the α-ß transition entropy. The comparison of experimental and theoretical approaches presented here provides a detailed picture of the lattice dynamics in these oxides beyond the zone center and shows that the accuracy of DFT is sufficient for future calculations of similar material structures.
RESUMO
Self-amplified spontaneous emission (SASE) enables X-ray free-electron lasers (XFELs) to generate hard X-ray pulses of sub-100 fs duration. However, due to the stochastic nature of SASE, the energy spectrum fluctuates from pulse to pulse. Many experiments that employ XFEL radiation require the resolution of the spectrum of each pulse. The work presented here investigates the capacity of a thin strongly bent diamond crystal to resolve the energy spectra of hard X-ray SASE pulses by studying its diffraction properties. Rocking curves of the symmetric C*(440) reflection have been measured for different bending radii. The experimental data match the theoretical modelling based on the Takagi-Taupin equations of dynamical diffraction. A uniform strain gradient has proven to be a valid model of strain deformations in the crystal.
RESUMO
Hard-x-ray spectroscopy relies on a suite of modern techniques for studies of vibrational, electronic, and magnetic excitations in condensed matter. At present, the energy resolution of these techniques can be improved only by decreasing the spectral window of the involved optics-monochromators and analyzers-thereby sacrificing the intensity. Here, we demonstrate hard-x-ray spectroscopy with greatly improved energy resolution without narrowing the spectral window by adapting principles of spectrographic imaging to the hard-x-ray regime. Similar to Newton's classical prism, the hard-x-ray spectrograph disperses different "colors"-i.e., energies-of x-ray photons in space. Then, selecting each energy component with a slit ensures high energy resolution, whereas measuring x-ray spectra with all components of a broad spectral window keeps the intensity. We employ the principles of spectrographic imaging for phonon spectroscopy. Here the new approach revealed anomalous soft atomic dynamics in α-iron, a phenomenon which was not previously reported in the literature. We argue that hard-x-ray spectrographic imaging also could be a path to discovering new physics in studies of electronic and magnetic excitations.
RESUMO
Mössbauer reflectivity spectra and nuclear resonance reflectivity (NRR) curves have been measured using the Synchrotron Mössbauer Source (SMS) for a [57Fe/Cr]30 periodic multilayer, characterized by the antiferromagnetic interlayer coupling between adjacent 57Fe layers. Specific features of the Mössbauer reflectivity spectra measured with π-polarized radiation of the SMS near the critical angle and at the `magnetic' maximum on the NRR curve are analyzed. The variation of the ratio of lines in the Mössbauer reflectivity spectra and the change of the intensity of the `magnetic' maximum under an applied external field has been used to reveal the transformation of the magnetic alignment in the investigated multilayer.
RESUMO
Metallic phases in the Tazewell IIICD iron and Esquel pallasite meteorites were examined using 57Fe synchrotron Mössbauer spectroscopy. Spatial resolution of ~10-20 µm was achieved, together with high throughput, enabling individual spectra to be recorded in less than 1 h. Spectra were recorded every 5-10 µm, allowing phase fractions and hyperfine parameters to be traced along transects of key microstructural features. The main focus of the study was the transitional region between kamacite and plessite, known as the "cloudy zone." Results confirm the presence of tetrataenite and antitaenite in the cloudy zone as its only components. However, both phases were also found in plessite, indicating that antitaenite is not restricted exclusively to the cloudy zone, as previously thought. The confirmation of paramagnetic antitaenite as the matrix phase of the cloudy zone contrasts with recent observations of a ferromagnetic matrix phase using X-ray photoemission electron spectroscopy. Possible explanations for the different results seen using these techniques are proposed.
RESUMO
Group velocity control is demonstrated for x-ray photons of 14.4 keV energy via a direct measurement of the temporal delay imposed on spectrally narrow x-ray pulses. Subluminal light propagation is achieved by inducing a steep positive linear dispersion in the optical response of 57Fe Mössbauer nuclei embedded in a thin film planar x-ray cavity. The direct detection of the temporal pulse delay is enabled by generating frequency-tunable spectrally narrow x-ray pulses from broadband pulsed synchrotron radiation. Our theoretical model is in good agreement with the experimental data.
RESUMO
Evolution of structure and local magnetic fields in (Fe(1-x)Co(x))76Mo8Cu1B15 (HITPERM) metallic glass ribbons with various amounts of Co (x = 0, 0.25, 0.5) were studied in situ using diffraction and nuclear forward scattering of synchrotron radiation. It was found that crystallization of all three glasses proceeds in two stages. In the first stage, bcc (Fe,Co) nanocrystals are formed, while in the second stage additional crystalline phases evolve. For all three glasses, the crystallization temperatures at the wheel side were found to be lower than at the air side of the ribbon. The crystallization temperatures were found to decrease with increasing Co content. The lattice parameters of the bcc nanocrystals decrease up to about 550 °C and then increase pointing to squeezing Mo atoms out of the nanograins or to interface effects between the nanocrystals and the glassy matrix. Nuclear forward scattering enabled separate evaluation of the contributions that stem from structurally different regions within the investigated samples including the newly formed nanocrystals and the residual amorphous matrix. Even minor Co content (x = 0.25) has a substantial effect not only upon the magnetic behaviour of the alloy but also upon its structure. Making use of hyperfine magnetic fields, it was possible to unveil structurally diverse positions of Fe atoms that reside in a nanocrystalline lattice with different numbers of Co nearest neighbours.
RESUMO
The performance of a cryogenically cooled double-crystal silicon monochromator was studied under high-heat-load conditions with total absorbed powers and power densities ranging from 8 to 780â W and from 8 to 240â Wâ mm(-2), respectively. When the temperature of the first crystal is maintained close to the temperature of zero thermal expansion of silicon, the monochromator shows nearly ideal performance with a thermal slope error of 0.6â µrad. By tuning the size of the first slit, the regime of the ideal performance can be maintained over a wide range of heat loads, i.e. from power densities of 110â Wâ mm(-2) (at total absorbed power of 510â W) to 240â Wâ mm(-2) (at total absorbed power of 240â W).
RESUMO
The design of a (57)Fe Synchrotron Mössbauer Source (SMS) for energy-domain Mössbauer spectroscopy using synchrotron radiation at the Nuclear Resonance beamline (ID18) at the European Synchrotron Radiation Facility is described. The SMS is based on a nuclear resonant monochromator employing pure nuclear reflections of an iron borate ((57)FeBO(3)) crystal. The source provides (57)Fe resonant radiation at 14.4â keV within a bandwidth of 15â neV which is tunable in energy over a range of about ±0.6â µeV. In contrast to radioactive sources, the beam of γ-radiation emitted by the SMS is almost fully resonant and fully polarized, has high brilliance and can be focused to a 10â µm × 5â µm spot size. Applications include, among others, the study of very small samples under extreme conditions, for example at ultrahigh pressure or combined high pressure and high temperature, and thin films under ultrahigh vacuum. The small cross section of the beam and its high intensity allow for rapid collection of Mössbauer data. For example, the measuring time of a spectrum for a sample in a diamond anvil cell at â¼100â GPa is around 10â min, whereas such an experiment with a radioactive point source would take more than one week and the data quality would be considerably less. The SMS is optimized for highest intensity and best energy resolution, which is achieved by collimation of the incident synchrotron radiation beam and thus illumination of the high-quality iron borate crystal within a narrow angular range around an optimal position of the rocking curve. The SMS is permanently located in an optics hutch and is operational immediately after moving it into the incident beam. The SMS is an in-line monochromator, i.e. the beam emitted by the SMS is directed almost exactly along the incident synchrotron radiation beam. Thus, the SMS can be easily utilized with all existing sample environments in the experimental hutches of the beamline. Owing to a very strong suppression of electronic scattering for pure nuclear reflections (â¼10(-9)), SMS operation does not required any gating of the prompt electronic scattering. Thus, the SMS can be utilized in any mode of storage ring operation.
RESUMO
The vibrational properties of the cationic spin crossover (SCO) coordination polymers [{Fe(4-amino-1,2,4-triazole)(3)}(+2)](n) containing the anions chlorine, methanosulfonate and 1-naphthalenesulfonate have been studied via nuclear inelastic scattering of synchrotron radiation (NIS) as well as by Raman spectroscopy. Although the different anions have a strong influence on the spin crossover temperature, they have little effect on the positions of the spin marker bands in the NIS and Raman spectra. By comparing the line positions of the NIS spin marker bands with those observed by Raman spectroscopy, it has been possible to distinguish vibrations symmetry (A(u) or A(g)) because modes of A(u) and A(g) symmetries are NIS active, but only the A(g) modes are Raman active. The normal mode analysis of charge compensated cationic pentameric and hexameric model structures which have been obtained by density functional calculations reproduces the experimentally observed mode frequencies and the geometry optimization reproduces iron-ligand distances reported for these and related SCO coordination complexes. The effect of charge compensation appears to be independent of the choice of the functional and the basis set which shows that DFT calculations using B3LYP in conjunction with the basis set CEP-31G are a time effective approach in order to study vibrational properties of Fe(II) SCO compounds.
Assuntos
Compostos Ferrosos/química , Polímeros/química , Teoria Quântica , Modelos Moleculares , Análise Espectral Raman , VibraçãoRESUMO
The spatial confinement of atoms at surfaces and interfaces significantly alters the lattice dynamics of thin films, heterostructures and multilayers. Ultrathin films with high dielectric constants (high-k) are of paramount interest for applications as gate layers in current and future integrated circuits. Here we report a lattice dynamics study of high-k Eu2O3 films with thicknesses of 21.3, 2.2, 1.3, and 0.8 nm deposited on YSZ(001). The Eu-partial phonon density of states (PDOS), obtained from nuclear inelastic scattering, exhibits broadening of the phonon peaks accompanied by up to a four-fold enhancement of the number of low-energy states compared to the ab initio calculated PDOS of a perfect Eu2O3 crystal. Our analysis demonstrates that while the former effect reflects the reduced phonon lifetimes observed in thin films due to scattering from lattice defects, the latter phenomenon arises from an ultrathin EuO layer formed between the thin Eu2O3 film and the YSZ(001) substrate. Thus, our work uncovers another potential source of vibrational anomalies in thin films and multilayers, which has to be cautiously considered.
RESUMO
Spin crossover complexes are among the most studied classes of molecular switches and have attracted considerable attention for their potential technological use as active units in multifunctional devices. A fundamental step toward their practical implementation is the integration in macroscopic devices adopting hybrid vertical architectures. First, the physical properties of technological interest shown by these materials in the bulk phase have to be retained once they are deposited on a solid surface. Herein, we describe the study of a hybrid molecular inorganic junction embedding the spin crossover complex [Fe(qnal)2] (qnal = quinoline-naphthaldehyde) as an active switchable thin film sandwiched within energy-optimized metallic electrodes. In these junctions, developed and characterized with the support of state of the art techniques including synchrotron Mössbauer source (SMS) spectroscopy and focused-ion beam scanning transmission electron microscopy, we observed that the spin state conversion of the Fe(II)-based spin crossover film is associated with a transition from a space charge-limited current (SCLC) transport mechanism with shallow traps to a SCLC mechanism characterized by the presence of an exponential distribution of traps concomitant with the spin transition temperature.
RESUMO
Reducing the material sizes to the nanometer length scale leads to drastic modifications of the propagating lattice excitations (phonons) and their interactions with electrons and magnons. In EuO, a promising material for spintronic applications in which a giant spin-phonon interaction is present, this might imply a reduction of the degree of spin polarization in thin films. Therefore, a comprehensive investigation of the lattice dynamics and spin-phonon interaction in EuO films is necessary for practical applications. We report a systematic lattice dynamics study of ultrathin EuO(001) films using nuclear inelastic scattering on the Mössbauer-active isotope 151Eu and first-principles theory. The films were epitaxially grown on YAlO3(110), which induces a tensile strain of ca. 2%. By reducing the EuO layer thickness from 8 nm to a sub-monolayer coverage, the Eu-partial phonon density of states (PDOS) reveals a gradual enhancement of the number of low-energy phonon states and simultaneous broadening and suppression of the peaks. These deviations from bulk features lead to significant anomalies in the vibrational thermodynamic and elastic properties calculated from the PDOS. The experimental results, supported by first-principles theory, unveil a reduction of the strength of the spin-phonon interaction in the tensile-strained EuO by a factor of four compared to a strain-free lattice.
RESUMO
A multifunctional ultrahigh vacuum (UHV) system has been set up at the nuclear resonance beamline ID18 of the European Synchrotron Radiation Facility (ESRF). Thin and ultrathin films, nanoislands and -wires, multilayers, and stoichiometric oxides can be prepared by molecular beam epitaxy and characterized by low-energy electron diffraction, Auger electron spectroscopy, and reflection high-energy electron diffraction. Upon characterization the sample is transferred under UHV conditions to the chamber for experiments with the synchrotron beam. Electronic and magnetic properties, vibrational dynamics, and diffusion phenomena can be investigated by several synchrotron radiation based techniques, such as nuclear forward scattering, nuclear inelastic and quasielastic scattering, synchrotron radiation based perturbed angular correlations, and nuclear and electronic reflectivity. In addition, two portable UHV chambers serve to transfer the sample to other beamlines profiting from the available experimental techniques at the ESRF.
RESUMO
The use of single molecule magnets (SMMs) as cornerstone elements in spintronics and quantum computing applications demands that magnetic bistability is retained when molecules are interfaced with solid conducting surfaces. Here, we employ synchrotron Mössbauer spectroscopy to investigate a monolayer of a tetrairon(III) (Fe4) SMM chemically grafted on a gold substrate. At low temperature and zero magnetic field, we observe the magnetic pattern of the Fe4 molecule, indicating slow spin fluctuations compared to the Mössbauer timescale. Significant structural deformations of the magnetic core, induced by the interaction with the substrate, as predicted by ab initio molecular dynamics, are also observed. However, the effects of the modifications occurring at the individual iron sites partially compensate each other, so that slow magnetic relaxation is retained on the surface. Interestingly, these deformations escaped detection by conventional synchrotron-based techniques, like X-ray magnetic circular dichroism, thus highlighting the power of synchrotron Mössbauer spectroscopy for the investigation of hybrid interfaces.