Resonant X-ray excitation of the nuclear clock isomer 45Sc.

Resonant oscillators with stable frequencies and large quality factors help us to keep track of time with high precision. Examples range from quartz crystal oscillators in wristwatches to atomic oscillators in atomic clocks, which are, at present, our most precise time measurement devices1. The search for more stable and convenient reference oscillators is continuing2-6. Nuclear oscillators are better than atomic oscillators because of their naturally higher quality factors and higher resilience against external perturbations7-9. One of the most promising cases is an ultra-narrow nuclear resonance transition in 45Sc between the ground state and the 12.4-keV isomeric state with a long lifetime of 0.47 s (ref. 10). The scientific potential of 45Sc was realized long ago, but applications require 45Sc resonant excitation, which in turn requires accelerator-driven, high-brightness X-ray sources11 that have become available only recently. Here we report on resonant X-ray excitation of the 45Sc isomeric state by irradiation of Sc-metal foil with 12.4-keV photon pulses from a state-of-the-art X-ray free-electron laser and subsequent detection of nuclear decay products. Simultaneously, the transition energy was determined as [Formula: see text] with an uncertainty that is two orders of magnitude smaller than the previously known values. These advancements enable the application of this isomer in extreme metrology, nuclear clock technology, ultra-high-precision spectroscopy and similar applications.

Coherent X-ray-optical control of nuclear excitons.

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.

Evolution of the magnetic hyperfine field profiles in an ion-irradiated Fe60Al40 film measured by nuclear resonant reflectivity.

Nuclear resonant reflectivity (NRR) from an Fe60Al40 film was measured using synchrotron radiation at several grazing angles near the critical angle of total external reflection. Using laterally resolved measurements after irradiation with 20 keV Ne+ ions of gradually varying fluence of 0-3.0 × 1014 ions cm-2, the progressive creation of the ferromagnetic A2 phase with increasing ion fluence was confirmed. The observed depth selectivity of the method has been explained by application of the standing wave approach. From the time spectra of the nuclear resonant scattering in several reflection directions the depth profiles for different hyperfine fields were extracted. The results show that the highest magnetic hyperfine fields (∼18-23 T) are initially created in the central part of the film and partially at the bottom interface with the SiO2 substrate. The evolution of the ferromagnetic onset, commencing at a fixed depth within the film and propagating towards the interfaces, has been directly observed. At higher fluence (3.0 × 1014 ions cm-2) the depth distribution of the ferromagnetic fractions became more homogeneous across the film depth, in accordance with previous results.

Advanced X-ray polarimeter design for nuclear resonant scattering.

This work presents the improvements in the design and testing of polarimeters based on channel-cut crystals for nuclear resonant scattering experiments at the 14.4 keV resonance of 57Fe. By using four asymmetric reflections at asymmetry angles of α1 = -28°, α2 = 28°, α3 = -28° and α4 = 28°, the degree of polarization purity could be improved to 2.2 × 10-9. For users, an advanced polarimeter without beam offset is now available at beamline P01 of the storage ring PETRA III.

IRIXS: a resonant inelastic X-ray scattering instrument dedicated to X-rays in the intermediate energy range.

A new resonant inelastic X-ray scattering (RIXS) instrument has been constructed at beamline P01 of the PETRA III synchrotron. This instrument has been named IRIXS (intermediate X-ray energy RIXS) and is dedicated to X-rays in the tender-energy regime (2.5-3.5 keV). The range covers the L2,3 absorption edges of many of the 4d elements (Mo, Tc, Ru, Rh, Pd and Ag), offering a unique opportunity to study their low-energy magnetic and charge excitations. The IRIXS instrument is currently operating at the Ru L3-edge (2840 eV) but can be extended to the other 4d elements using the existing concept. The incoming photons are monochromated with a four-bounce Si(111) monochromator, while the energy analysis of the outgoing photons is performed by a diced spherical crystal analyzer featuring (102) lattice planes of quartz (SiO2). A total resolution of 100 meV (full width at half-maximum) has been achieved at the Ru L3-edge, a number that is in excellent agreement with ray-tracing simulations.

High-pressure nuclear inelastic scattering with backscattering monochromatization.

The capability to perform high-pressure low-temperature nuclear inelastic scattering on 125Te and 121Sb with a sapphire backscattering monochromator is presented. This technique was applied to measure nuclear inelastic scattering in TeO2 at pressures up to 10 GPa and temperatures down to 25 K. The evaluated partial Te densities of phonon states were compared with theoretical calculations and with Raman scattering measured under the same conditions. The high-pressure cell developed in this work can also be used for other techniques at pressures up to at least 100 GPa.

Elucidating the Structural Composition of an Fe-N-C Catalyst by Nuclear- and Electron-Resonance Techniques.

Fe-N-C catalysts are very promising materials for fuel cells and metal-air batteries. This work gives fundamental insights into the structural composition of an Fe-N-C catalyst and highlights the importance of an in-depth characterization. By nuclear- and electron-resonance techniques, we are able to show that even after mild pyrolysis and acid leaching, the catalyst contains considerable fractions of α-iron and, surprisingly, iron oxide. Our work makes it questionable to what extent FeN4 sites can be present in Fe-N-C catalysts prepared by pyrolysis at 900 °C and above. The simulation of the iron partial density of phonon states enables the identification of three FeN4 species in our catalyst, one of them comprising a sixfold coordination with end-on bonded oxygen as one of the axial ligands.

Electromagnetically induced transparency with resonant nuclei in a cavity.

The manipulation of light-matter interactions by quantum control of atomic levels has had a profound impact on optical sciences. Such manipulation has many applications, including nonlinear optics at the few-photon level, slow light, lasing without inversion and optical quantum information processing. The critical underlying technique is electromagnetically induced transparency, in which quantum interference between transitions in multilevel atoms renders an opaque medium transparent near an atomic resonance. With the advent of high-brilliance, accelerator-driven light sources such as storage rings or X-ray lasers, it has become attractive to extend the techniques of optical quantum control to the X-ray regime. Here we demonstrate electromagnetically induced transparency in the regime of hard X-rays, using the 14.4-kiloelectronvolt nuclear resonance of the Mössbauer isotope iron-57 (a two-level system). We exploit cooperative emission from ensembles of the nuclei, which are embedded in a low-finesse cavity and excited by synchrotron radiation. The spatial modulation of the photonic density of states in a cavity mode leads to the coexistence of superradiant and subradiant states of nuclei, respectively located at an antinode and a node of the cavity field. This scheme causes the nuclei to behave as effective three-level systems, with two degenerate levels in the excited state (one of which can be considered metastable). The radiative coupling of the nuclear ensembles by the cavity field establishes the atomic coherence necessary for the cancellation of resonant absorption. Because this technique does not require atomic systems with a metastable level, electromagnetically induced transparency and its applications can be transferred to the regime of nuclear resonances, establishing the field of nuclear quantum optics.

Nuclear Resonant Surface Diffraction of Synchrotron Radiation.

Nuclear resonant x-ray diffraction in grazing incidence geometry is used to determine the lateral magnetic configuration in a one-dimensional lattice of ferromagnetic nanostripes. During magnetic reversal, strong nuclear superstructure diffraction peaks appear in addition to the electronic ones due to an antiferromagnetic order in the nanostripe lattice. We show that the analysis of the angular distribution together with the time dependence of the resonantly diffracted x rays reveals surface spin structures with very high sensitivity. This scattering technique provides unique access to laterally correlated spin configurations in magnetically ordered nanostructures and, in perspective, also to their dynamics.

Nuclear inelastic scattering and density functional theory studies of a one-dimensional spin crossover [Fe(1,2,4-triazole)2(1,2,4-triazolato)](BF4) molecular chain.

Nuclear inelastic scattering (NIS) experiments have been performed in order to study the vibrational dynamics of the low- and high-spin states of the polynuclear 1D spin crossover compound [Fe(1,2,4-triazole)2(1,2,4-triazolato)](BF4) (1). Density functional theory (DFT) calculations using the functional B3LYP* and the basis set CEP-31G for heptameric and nonameric models of the compound yielded the normal vibrations and electronic energies for high-spin and low-spin isomers of three models differing in the distribution of anionic trz- ligands and BF4- anions. On the basis of the obtained energies a structural model with a centrosymmetric Fe(trzH)4(trz-)2 coordination core of the mononuclear unit of the chain is proposed. The obtained distribution of the BF4- counteranions in the proposed structure is similar to that obtained on the basis of X-ray powder diffraction studies by Grossjean et al. (Eur. J. Inorg. Chem., 2013, 796). The NIS data of the system diluted to 10% Fe(ii) content in a 90% Zn(ii) matrix (compound (2)) show a characteristic change of the spectral pattern of the low-spin centres, compared to the low-spin phase of the parent Fe(ii) complex (1). DFT calculations reveal that this is caused by a change of the structure of the neighbours of the low-spin centres. The spectral pattern of the high-spin centres in (2) is within a good approximation identical to that of the high-spin Fe(ii) isomer of (1). The inspection of the molecular orbitals of the monomeric model systems of [Fe(trzH)4(trz-)2] and [Fe(trzH)6], together with calculations of spin transition energies, point towards the importance of an electrostatic effect caused by the negatively charged ligands. This results in the stabilisation of the low-spin state of the complex containing the anionic ligand and shortening of the Fe-N(trz-) compared to the Fe-N(trzH) bond in high-spin, but not in low-spin [Fe(trzH)4(trz-)2].

Resonant inelastic X-ray scattering spectrometer with 25 meV resolution at the Cu K-edge.

An unparalleled resolution is reported with an inelastic X-ray scattering instrument at the Cu K-edge. Based on a segmented concave analyzer, featuring single-crystal quartz (SiO2) pixels, the spectrometer delivers a resolution near 25 meV (FWHM) at 8981 eV. Besides the quartz analyzer, the performance of the spectrometer relies on a four-bounce Si(553) high-resolution monochromator and focusing Kirkpatrick-Baez optics. The measured resolution agrees with the ray-tracing simulation of an ideal spectrometer. The performance of the spectrometer is demonstrated by reproducing the phonon dispersion curve of a beryllium single-crystal.

Influence of higher harmonics of the undulator in X-ray polarimetry and crystal monochromator design.

The spectrum of the undulator radiation of beamline P01 at Petra III has been measured after passing a multiple reflection channel-cut polarimeter. Odd and even harmonics up to the 15th order, as well as Compton peaks which were produced by the high harmonics in the spectrum, could been measured. These additional contributions can have a tremendous influence on the performance of the polarimeter and have to be taken into account for further polarimeter designs.

Spin precession mapping at ferromagnetic resonance via nuclear resonant scattering of synchrotron radiation.

We probe the spin dynamics in a thin magnetic film at ferromagnetic resonance by nuclear resonant scattering of synchrotron radiation at the 14.4 keV resonance of ^{57}Fe. The precession of the magnetization leads to an apparent reduction of the magnetic hyperfine field acting at the ^{57}Fe nuclei. The spin dynamics is described in a stochastic relaxation model adapted to the ferromagnetic resonance theory by Smit and Beljers to model the decay of the excited nuclear state. From the fits of the measured data, the shape of the precession cone of the spins is determined. Our results open a new perspective to determine magnetization dynamics in layered structures with very high depth resolution by employing ultrathin isotopic probe layers.

Tunable Subluminal Propagation of Narrow-band X-Ray Pulses.

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.

Direct evidence of Fe(V) and Fe(IV) intermediates during reduction of Fe(VI) to Fe(III): a nuclear forward scattering of synchrotron radiation approach.

Identification of unstable high-valent iron species in electron transfer reactions of ferrate(VI) (Fe(VI)O4(2-), Fe(VI)) has been an important challenge in advancing the understanding of the oxidative mechanisms of ferrates. This paper presents the first example of distinguishing various phases differing in the valence state of iron in the solid state reduction of Fe(VI) to Fe(III) oxides at 235 °C using hyperfine parameters, isomer shift and hyperfine magnetic field, obtained from nuclear forward scattering of synchrotron radiation (NFS). The NFS technique enables a fast data accumulation resulting in high time resolution of in situ experiments. The results suggest a reaction mechanism, involving Fe(V) and Fe(IV) species, in the thermal decomposition of K2FeO4 to KFeO2. The present study opens up an approach to exploring the unambiguous identification of Fe(VI), Fe(V), Fe(IV), and Fe(III) in electron-transfer reaction mechanisms of ferrates in solid and aqueous phase systems.

Isoprenoid Biosynthesis in Pathogenic Bacteria: Nuclear Resonance Vibrational Spectroscopy Provides Insight into the Unusual [4Fe-4S] Cluster of the E.†coli LytB/IspH Protein.

The LytB/IspH protein catalyzes the last step of the methylerythritol phosphate (MEP) pathway which is used for the biosynthesis of essential terpenoids in most pathogenic bacteria. Therefore, the MEP pathway is a target for the development of new antimicrobial agents as it is essential for microorganisms, yet absent in humans. Substrate-free LytB has a special [4Fe-4S](2+) cluster with a yet unsolved structure. This motivated us to use synchrotron-based nuclear resonance vibrational spectroscopy (NRVS) in combination with quantum chemical-molecular mechanical (QM/MM) calculations to gain more insight into the structure of substrate-free LytB. The apical iron atom of the [4Fe-4S](2+) is clearly linked to three water molecules. We additionally present NRVS data of LytB bound to its natural substrate, (E)-4-hydroxy-3-methylbut-2-en-1-yl diphosphate (HMBPP) and to the inhibitors (E)-4-amino-3-methylbut-2-en-1-yl diphosphate and (E)-4-mercapto-3-methylbut-2-en-1-yl diphosphate.

Vacuum-assisted generation and control of atomic coherences at x-ray energies.

The control of light-matter interaction at the quantum level usually requires coherent laser fields. But already an exchange of virtual photons with the electromagnetic vacuum field alone can lead to quantum coherences, which subsequently suppress spontaneous emission. We demonstrate such spontaneously generated coherences (SGC) in a large ensemble of nuclei operating in the x-ray regime, resonantly coupled to a common cavity environment. The observed SGC originates from two fundamentally different mechanisms related to cooperative emission and magnetically controlled anisotropy of the cavity vacuum. This approach opens new perspectives for quantum control, quantum state engineering and simulation of quantum many-body physics in an essentially decoherence-free setting.

The synchrotron radiation source PETRA III and its future ultra-low-emittance upgrade PETRA IV.

PETRA III at DESY is one of the brightest synchrotron radiation sources worldwide. It serves a broad international multidisciplinary user community from academia to industry at currently 25 specialised beamlines. With a storage-ring energy of 6 GeV, it provides mainly hard to high-energy X-rays for versatile experiments in a very broad range of scientific fields. It is ideally suited for an upgrade to the ultra-low emittance source PETRA IV, owing to its large circumference of 2304 m. With a targeted storage ring emittance of 20 × 5 pm 2 rad 2 , PETRA IV will reach spectral brightnesses two to three orders of magnitude higher than today. The unique beam parameters will make PETRA IV the ultimate in situ 3D microscope for biological, chemical, and physical processes helping to address key questions in health, energy, mobility, information technology, and earth and environment.

Coherent control of collective nuclear quantum states via transient magnons.

Ultrafast and precise control of quantum systems at x-ray energies involves photons with oscillation periods below 1 as. Coherent dynamic control of quantum systems at these energies is one of the major challenges in hard x-ray quantum optics. Here, we demonstrate that the phase of a quantum system embedded in a solid can be coherently controlled via a quasi-particle with subattosecond accuracy. In particular, we tune the quantum phase of a collectively excited nuclear state via transient magnons with a precision of 1 zs and a timing stability below 50 ys. These small temporal shifts are monitored interferometrically via quantum beats between different hyperfine-split levels. The experiment demonstrates zeptosecond interferometry and shows that transient quasi-particles enable accurate control of quantum systems embedded in condensed matter environments.