X-ray Photon Correlation Spectroscopy Research Articles

Special Issue on Trends in Sub-Microsecond X-ray Science with Coherent Beams

Large increases in synchrotron brightness have brought notable breakthroughs in measurement techniques that exploit transverse coherence, such as X-ray photon correlation spectroscopy (XPCS), coherent diffraction imaging (CDI), diffraction microscopy, and ptychography [...]

Towards a Counting Point Detector for Nanosecond Coherent X-ray Science

We present the technical realization of a high-speed hard X-ray single-photon counting-detection scheme based on a commercial avalanche silicon photodiode and high-speed oscilloscope. The development is motivated by the need to perform pulse-resolved photon-correlation and pump-probe studies at synchrotron sources with densely packed pulse patterns that result in high repetition rate pulses on the order of hundreds of MHz. Commissioning experiments are performed at the 1C PAL-KRISS beamline at PLS-II of South Korea operating at a burst mode maximum repetition rate of 500 MHz. In such a high count-rate measurement, detector dead-time can lead to a distortion of counting statistics. We are able to model the counting behavior of our detector under these conditions with a detector dead-time comparable to time between X-ray pulses, implying that nanosecond X-ray photon correlation spectroscopy should be possible at diffraction-limited light sources.

Emergent dynamics of light-induced active colloids probed by XPCS

Self-propelled particulate systems manifest certain collective behavior of living matter, which have been the subject of intense research over the past decades. One of the elegant methods for realizing such active motions is by means of custom synthesized Janus particles suspended in a catalytic medium that can be triggered upon illumination by ultraviolet light. In this work, the evolution of the particle dynamics from passive diffusive to active ballistic behavior upon light illumination was probed by multispeckle x-ray photon correlation spectroscopy (XPCS). This technique enables not only studying the emergence of active motions in three dimensions (3D) but also deciphering different contributions to the overall dynamics. Using a combination of homodyne and heterodyne analysis, the ensemble averaged mean velocity, velocity fluctuations and diffusion coefficient of particles were determined in the thermodynamic limit. Results revealed a gradual transition from diffusive to ballistic dynamics with systematic increase of the catalytic activity. At the intermediate region, the dynamics is dominated by Gaussian velocity fluctuations and an enhanced relaxation rate with a weaker wave vector dependence similar to superdiffusive behavior. For the highest activity, the dynamics became purely ballistic with Lorentzian-like distribution of velocity fluctuations. Presented results demonstrate that different aspects of active dynamics can be investigated in 3D over a broad range of Péclet numbers and other control parameters by means of multispeckle XPCS.

Computational approaches to model X-ray photon correlation spectroscopy from molecular dynamics

X-ray photon correlation spectroscopy (XPCS) allows for the resolution of dynamic processes within a material across a wide range of length and time scales. X-ray speckle visibility spectroscopy (XSVS) is a related method that uses a single diffraction pattern to probe ultrafast dynamics. Interpretation of the XPCS and XSVS data in terms of underlying physical processes is necessary to establish the connection between the macroscopic responses and the microstructural dynamics. To aid the interpretation of the XPCS and XSVS data, we present a computational framework to model these experiments by computing the X-ray scattering intensity directly from the atomic positions obtained from molecular dynamics simulations. We compare the efficiency and accuracy of two alternative computational methods: the direct method computing the intensity at each diffraction vector separately, and a method based on fast Fourier transform that computes the intensities at all diffraction vectors at once. The computed X-ray speckle patterns capture the density fluctuations over a range of length and time scales and are shown to reproduce the known properties and relations of experimental XPCS and XSVS for liquids.

X-Ray Photon Correlation Spectroscopy Towards Measuring Nanoparticle Diameters in Biological Environments Allowing for the In Situ Analysis of their Bio-Nano Interface.

X-ray photon correlation spectroscopy (XPCS), a synchrotron source-based technique to measure sample dynamics, is used to determine hydrodynamic diameters of gold nanoparticles (Au NPs) of different sizes in biological environments. In situ determined hydrodynamic diameters are benchmarked with values obtained by dynamic light scattering. The technique is then applied to analyze the behavior of the Au NPs in a biological environment. First, a concentration-dependent agglomeration in the presence of NaCl is determined. Second, concentration-dependent increase in hydrodynamic diameter of the Au NPs upon the presence of proteins is determined. As X-rays in the used energy range are barely scattered by biological matter, dynamics of the Au NPs can be also detected in situ in complex biological environments, such as blood. These measurements demonstrate the possibility of XPCS for insitu analytics of nanoparticles (NPs) in biological environments where similar detection techniques based on visible light would severely suffer from scattering, absorption, and reflection effects.

Nanofocused x-ray photon correlation spectroscopy

Here, we demonstrate an experimental proof of concept for nanofocused x-ray photon correlation spectroscopy, a technique sensitive to nanoscale fluctuations present in a broad range of systems. The experiment, performed at the NanoMAX beamline at MAX IV, uses a novel event-based x-ray detector to capture nanoparticle structural dynamics with microsecond resolution. By varying the nanobeam size from σ=88 nm to σ=2.5μm, we quantify the effect of the nanofocus on the small-angle scattering lineshape and on the diffusion coefficients obtained from nano-XPCS. We observe that the use of nanobeams leads to a multifold increase in speckle contrast, which greatly improves the experimental signal-to-noise ratio, quantified from the two-time intensity correlation functions. We conclude that it is possible to account for influence of the high beam divergence on the lineshape and measured dynamics by including a convolution with the nanobeam profile in the model.Received 17 December 2021Revised 19 May 2022Accepted 16 June 2022DOI:https://doi.org/10.1103/PhysRevResearch.4.L032012Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Physical SystemsNanoparticlesSynchrotron radiation & free-electron lasersTechniquesCoherent X-ray scatteringX-ray photon correlation spectroscopyCondensed Matter, Materials & Applied PhysicsPolymers & Soft Matter

Microscopic dynamics underlying the stress relaxation of arrested soft materials

Arrested soft materials such as gels and glasses exhibit a slow stress relaxation with a broad distribution of relaxation times in response to linear mechanical perturbations. Although this macroscopic stress relaxation is an essential feature in the application of arrested systems as structural materials, consumer products, foods, and biological materials, the microscopic origins of this relaxation remain poorly understood. Here, we elucidate the microscopic dynamics underlying the stress relaxation of such arrested soft materials under both quiescent and mechanically perturbed conditions through X-ray photon correlation spectroscopy. By studying the dynamics of a model associative gel system that undergoes dynamical arrest in the absence of aging effects, we show that the mean stress relaxation time measured from linear rheometry is directly correlated to the quiescent superdiffusive dynamics of the microscopic clusters, which are governed by a buildup of internal stresses during arrest. We also show that perturbing the system via small mechanical deformations can result in large intermittent fluctuations in the form of avalanches, which give rise to a broad non-Gaussian spectrum of relaxation modes at short times that is observed in stress relaxation measurements. These findings suggest that the linear viscoelastic stress relaxation in arrested soft materials may be governed by nonlinear phenomena involving an interplay of internal stress relaxations and perturbation-induced intermittent avalanches.

Observation of Collective Molecular Dynamics in a Chalcogenide Glass: Results from X-ray Photon Correlation Spectroscopy.

The structural relaxation processes in a Ge3As52S45 molecular chalcogenide glass sample were directly studied by X-ray photon correlation spectroscopy (XPCS). XPCS was conducted at the first sharp diffraction peak at q = 1.16 Å-1 at temperatures ranging from 123 K to above the glass transition at 328 K, and the results showed two different dynamical regimes. At a low temperature, the observed glass dynamics are slow and dominated by X-ray-photon-induced effects, which are temperature independent. At a higher temperature, we observed a dramatic decrease in the fluctuation timescales, indicating that the dynamics were mainly due to the intermolecular correlation of the As4S3 molecule in the glass. The timescales in this high-temperature range agree well with those determined from measurements of the Newtonian viscosity. Our XPCS studies suggest an extended length scale of the relaxation process in glassy Ge3As52S45 from the single molecule to the intermolecular range across the glass transition, providing a unique direct probe of the dynamics beyond the length scales of the individual molecule.

Photon correlation spectroscopy with heterodyne mixing based on soft x-ray magnetic circular dichroism

Many magnetic equilibrium states and phase transitions are characterized by fluctuations. Such magnetic fluctuation can in principle be detected with scattering-based x-ray photon correlation spectroscopy (XPCS). However, in the established approach of XPCS, the magnetic scattering signal is quadratic in the magnetic scattering cross section, which results not only in often prohibitively small signals but also in a fundamental inability to detect negative correlations (anticorrelations). Here, we propose to exploit the possibility of heterodyne mixing of the magnetic signal with static charge scattering to reconstruct the first-order (linear) magnetic correlation function. We show that the first-order magnetic scattering signal reconstructed from heterodyne scattering now directly represents the underlying magnetization texture. Moreover, we suggest a practical implementation based on an absorption mask rigidly connected to the sample, which not only produces a static charge scattering signal but also eliminates the problem of drift-induced artificial decay of the correlation functions. Our method thereby significantly broadens the range of scientific questions accessible by magnetic x-ray photon correlation spectroscopy.

Structural and dynamical aspects of extremely swollen lyotropic phases

In this contribution, the composition-temperature phase diagram of a swollen microemulsion system was investigated using high resolution small-angle X-ray scattering to explore the morphological landscape over the selected region of interest. As the oil content was increased, the morphology transformed from a bicontinuous microemulsion, XD < 0.6, to a disordered emulsified-microemulsion, XD > 0.6, consisting of a dense packing of microemulsion droplets, and a hexagonal phase at XD = 0.6. During the heating from room temperature up to the highest temperature, T = 304 K, each composition transitioned into the disordered emulsified-microemulsion morphology, however, while cooling more complex structural changes were observed. Interestingly, for each composition the same sequence of phase transitions was observed during the cooling process, first there was a transition to the emulsified hexagonal phase and then to the bicontinuous microemulsion, likely due to further expulsion of oil, resulting in a composition that would favour a bicontinuous morphology. The dynamics of the microemulsion droplets were probed using X-ray photon correlation spectroscopy, which revealed two relaxation modes, typically found in dense colloidal systems below their glass transition. These results demonstrate the importance of a combined structural and dynamical approach in the studies of dense microemulsion systems, relevant for many industrial applications.

PyXPCSviewer: an open-source interactive tool for X-ray photon correlation spectroscopy visualization and analysis.

pyXPCSviewer, a Python-based graphical user interface that is deployed at beamline 8-ID-I of the Advanced Photon Source for interactive visualization of XPCS results, is introduced. pyXPCSviewer parses rich X-ray photon correlation spectroscopy (XPCS) results into independent PyQt widgets that are both interactive and easy to maintain. pyXPCSviewer is open-source and is open to customization by the XPCS community for ingestion of diversified data structures and inclusion of novel XPCS techniques, both of which are growing demands particularly with the dawn of near-diffraction-limited synchrotron sources and their dedicated XPCS beamlines.

Relaxation and Aging of Nanosphere Assemblies at a Water-Oil Interface.

The relaxation and aging of an assembly of spherical nanoparticles (NPs) at a water-oil interface are characterized in situ by grazing incidence X-ray photon correlation spectroscopy. The dynamics of the interfacial assembly is measured while the interface saturates with NPs. Weak attractions between NPs lead to gel-like structures in the assembly, where the in-plane ordering is inhibited by the broad size distribution of the NPs. Structural rearrangements on the length scale of the NP-NP center-to-center distances proceed by intermittent fluctuations instead of continuous cooperative motions. The coexistence of rapid and slow NP populations is confirmed, as commonly observed in soft glass-forming materials. Dynamics are increasingly slowed as the NPs initially segregate to the locally clustered interface. The structural relaxation of the NPs in these localized clusters is 5 orders of magnitude slower than that of free particles in the bulk. When the interface is nearly saturated, the time for relaxation increases suddenly due to the onset of local jamming, and the dynamics slow exponentially afterward until the system reaches collective jamming by cooperative rearrangements. This investigation provides insights into structural relaxations near the glass transition and the evolution of the structure and dynamics of the assemblies as they transition from an isotropic liquid to a dense disordered film.

Reverse-engineering method for XPCS studies of non-equilibrium dynamics.

X-ray photon correlation spectroscopy (XPCS) is a powerful tool in the investigation of dynamics covering a broad time and length scale. It has been widely used to probe dynamics for systems in both equilibrium and non-equilibrium states; in particular, for systems undergoing a phase transition where the structural growth kinetics and the microscopic dynamics are strongly intertwined. The resulting time-dependent dynamic behavior can be described using the two-time correlation function (TTC), which, however, often contains more interesting features than the component along the diagonal, and cannot be easily interpreted via the classical simulation methods. Here, a reverse engineering (RE) approach is proposed based on particle-based heuristic simulations. This approach is applied to an XPCS measurement on a protein solution undergoing a liquid-liquid phase separation. It is demonstrated that the rich features of experimental TTCs can be well connected with the key control parameters including size distribution, concentration, viscosity and mobility of domains. The dynamic information obtained from this RE analysis goes beyond the existing theory. The RE approach established in this work is applicable for other processes such as film growth, coarsening or evolving systems.

Gelation Dynamics upon Pressure-Induced Liquid-Liquid Phase Separation in a Water-Lysozyme Solution.

Employing X-ray photon correlation spectroscopy, we measure the kinetics and dynamics of a pressure-induced liquid-liquid phase separation (LLPS) in a water-lysozyme solution. Scattering invariants and kinetic information provide evidence that the system reaches the phase boundary upon pressure-induced LLPS with no sign of arrest. The coarsening slows down with increasing quench depths. The g2 functions display a two-step decay with a gradually increasing nonergodicity parameter typical for gelation. We observe fast superdiffusive (γ ≥ 3/2) and slow subdiffusive (γ < 0.6) motion associated with fast viscoelastic fluctuations of the network and a slow viscous coarsening process, respectively. The dynamics age linearly with time τ ∝ tw, and we observe the onset of viscoelastic relaxation for deeper quenches. Our results suggest that the protein solution gels upon reaching the phase boundary.

Structure and anisotropic dynamics of stimuli responsive colloidal ellipsoids at the nearest neighbor length scale

Stimuli-responsive self-assembly of (an) isotropic colloids has resulted in a plethora of self-assembled structures with potential applications in fabricating smart materials. A lack of detailed understanding of the interplay between these self-assembled structures and the resulting dynamics has often impeded the exploitation of their full potential. Herein, we have unveiled the relationship between the field-driven self-assembled structures and the corresponding collective dynamics at the nearest neighbor length scale using X-ray photon correlation spectroscopy and magnetic colloidal ellipsoids. We demonstrate that the effective long-time collective diffusion coefficient, Deff(q), scales with the inverse of the scattered intensity for various stimuli-responsive self-assembled phases. At high-volume fraction, the system approaches a kinetically arrested state. The anisotropic slowdown of Deff(q) hints towards the formation of an oriented glass. Our approach opens new avenues for exploring the stimuli-responsive dynamics of strongly interacting colloidal systems with diverse shapes and properties.

Microscopic Dynamics of Inverse Wormlike Micelles Probed Using X-ray Photon Correlation Spectroscopy.

Wormlike micelles (WLMs) are ubiquitous viscoelastic modifiers that share properties with polymer solutions. While their macroscopic rheology is well-understood, their microscopic dynamics remain difficult to measure because they span a large range of time and length scales. In this work, we demonstrate the use of X-ray photon correlation spectroscopy to interrogate the segmental dynamics of inverse WLM solutions swollen with a rubidium chloride solution. We observe a diffusive scaling of the dynamics and extract a temperature-dependent diffusion coefficient, which we associate with the thermal interactions of the slow segmental dynamics near entanglement points. We probe this relaxation process across the unbranched to branched topological transition and find no microstructural evidence of branch formation in the slow mode. Instead, we observe that the dynamics become more homogeneous and prominent as the temperature is reduced and water content increases.

X-ray induced dynamics in borate glasses with different network connectivity

Hard x rays induce atomic dynamics in oxide glasses at doses low enough that the average structure is unchanged. X-ray photon correlation spectroscopy is used here to study this effect in a series of alkali borate glasses characterized by different network connectivity. The product of the x-ray dose rate per atom and the decay time of the density correlation function is a sample-dependent parameter with the dimensions of an energy: It varies between a fraction of eV and few tens of eV and is sensitive to the network connectivity of the glass. It can then be used to access some bonding information also in cases where the x rays perturb the material, a regime of great interest in modern x-ray-based experiments.

Advancing Chemical Separations: Unraveling the Structure and Dynamics of Phase Splitting in Liquid-Liquid Extraction.

Liquid-liquid extraction (LLE), the go-to process for a variety of chemical separations, is limited by spontaneous organic phase splitting upon sufficient solute loading, called third phase formation. In this study we explore the applicability of critical phenomena theory to gain insight into this deleterious phase behavior with the goal of improving separations efficiency and minimizing waste. A series of samples representative of rare earth purification were constructed to include each of one light and one heavy lanthanide (cerium and lutetium) paired with one of two common malonamide extractants (DMDOHEMA and DMDBTDMA). The resulting postextraction organic phases are chemically complex and often form rich hierarchical structures whose statics and dynamics near the critical point were probed herein with small-angle X-ray scattering and high-speed X-ray photon correlation spectroscopy. Despite their different extraction behaviors, all samples show remarkably similar critical behavior with exponents well described by classical critical point theory consistent with the 3D Ising model, where the critical behavior is characterized by fluctuations with a single diverging length scale. This unexpected result indicates a significant reduction in relevant chemical parameters at the critical point, indicating that the underlying behavior of phase transitions in LLE rely on far fewer variables than are generally assumed. The obtained scalar order parameter is attributed to the extractant fraction of the extractant/diluent mixture, revealing that other solution components and their respective concentrations simply shift the critical temperature but do not affect the nature of the critical fluctuations. These findings point to an opportunity to drastically simplify studies of liquid-liquid phase separation and phase diagram development in general while providing insights into LLE process improvement.

Wave-optics simulation software for synchrotron radiation from 4th generation storage rings based on a coherent modes model.

The evolution from 3rd to 4th generation of storage rings significantly enhanced the coherence of synchrotron radiation sources, making coherent scattering techniques such as coherent X-ray diffraction imaging (CXDI) and X-ray photon correlation spectroscopy more accessible. In conformance with the design requirements of coherent beamlines at the High Energy Photon Source (HEPS), we have developed wave optics simulation software, the Coherence Analysis Toolbox, based on coherent modes decomposition and a wavefront propagation model. Simulations of beamline performance and a CXDI experiment on the hard X-ray coherent scattering beamline at HEPS were carried out. This software is open source and now available on GitHub.

Study on the Dynamics of Silica-filled Rubber Using X-ray Photon Correlation Spectroscopy

Study on the Dynamics of Silica-filled Rubber Using X-ray Photon Correlation Spectroscopy