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We report on the evolution of the charge density wave (CDW) and spin density wave (SDW) order of a chromium film following photoexcitation with an ultrafast optical laser pulse. The CDW is measured by ultrafast time-resolved x-ray diffraction of the CDW satellite that tracks the suppression and recovery of the CDW following photoexcitation. We find that as the temperature of the film approaches a discontinuous phase transition in the CDW and SDW order, the time scales of recovery increase exponentially from the expected thermal time scales. We extend a Landau model for SDW systems to account for this critical slowing with the appropriate boundary conditions imposed by the geometry of the thin film system. This model allows us to assess the energy barrier between available CDW/SDW states with different spatial periodicities., Comment: Author typo fixed

We use a 30-nm x-ray beam to study the spatially resolved properties of a SmNiO$_3$-based nanodevice that is doped with protons. The x-ray absorption spectra supported by density-functional theory (DFT) simulations show partial reduction of nickel valence in the region with high proton concentration, which leads to the insulating behavior. Concurrently, x-ray diffraction reveals only a small lattice distortion in the doped regions. Together, our results directly show that the knob which proton doping modifies is the electronic valency, and not the crystal lattice. The studies are relevant to on-going efforts to disentangle structural and electronic effects across metal-insulator phase transitions in correlated oxides.

Electronic instabilities drive ordering transitions in condensed matter. Despite many advances in the microscopic understanding of the ordered states, a more nuanced and profound question often remains unanswered: how do the collective excitations influence the electronic order formation? Here, we experimentally show that a phonon affects the spin density wave (SDW) formation after an SDW-quench by femtosecond laser pulses. In a thin film, the temperature-dependent SDW period is quantized, allowing us to track the out-of-equilibrium formation path of the SDW precisely. By exploiting its persistent coupling to the lattice, we probe the SDW through the transient lattice distortion, measured by femtosecond X-ray diffraction. We find that within 500 femtoseconds after a complete quench, the SDW forms with the low-temperature period, directly bypassing a thermal state with the high-temperature period. We argue that a momentum-matched phonon launched by the quench changes the formation path of the SDW through the dynamic pinning of the order parameter.

The discovery of novel phases of matter is at the core of modern physics. In quantum materials, subtle variations in atomic-scale interactions can induce dramatic changes in macroscopic properties and drive phase transitions. Despite their importance, the mesoscale processes underpinning phase transitions often remain elusive because of the vast differences in timescales between atomic and electronic changes and thermodynamic transformations. Here, we photoinduce and directly observe with x-ray scattering an ultrafast enhancement of the structural long-range order in the archetypal Mott system V2O3. Despite the ultrafast change in crystal symmetry, the change of unit cell volume occurs an order of magnitude slower and coincides with the insulator-to-metal transition. The decoupling between the two structural responses in the time domain highlights the existence of a transient photoinduced precursor phase, which is distinct from the two structural phases present in equilibrium. X-ray nanoscopy reveals that acoustic phonons trapped in nanoscale blocks govern the dynamics of the ultrafast transition into the precursor phase, while nucleation and growth of metallic domains dictate the duration of the slower transition into the metallic phase. The enhancement of the long-range order before completion of the electronic transition demonstrates the critical role the non-equilibrium structural phases play during electronic phase transitions in correlated electrons systems.

Multi-electron transfer processes, such as hydrogen and oxygen evolution reactions, are crucially important in energy and biological science but require favorable catalysts to achieve fast kinetics. Nanostructuring catalysts can dramatically improve their properties, which can be difficult to understand due to strain and size dependent thermodynamics, the influence of defects, and substrate dependent activities. Here, we report 3D imaging of single gold nanoparticles during catalysis of ascorbic acid decomposition using Bragg coherent diffractive imaging (BCDI) as a route to eliminate ensemble effects while elucidating the strain-activity connection. Local strains were measured in single nanoparticles and modeled using reactive molecular dynamics (RMD) simulations and finite element analysis (FEA) simulations. RMD reveals a new chemical pathway for local strain generation in the gold lattice: chemisorption of hydroxyl ions. FEA reveals that the RMD results are transferable to the larger nanocrystal sizes studied in the experiment. Our study reveals the strain-activity connection and opens a powerful new avenue for joint theoretical and experimental studies of multi-electron transfer processes catalyzed by nanocrystals., Comment: 17 pages, 4 figures

We used coherent light scattering in a multi-speckle detection scheme to investigate the mesoscale dynamics in aqueous foam. Time-resolved correlation of the scattered speckle intensities reveals the details of foam dynamics during aging. We introduce Temporal Contrast Analysis, a novel statistical tool that can be effective in characterizing structural rearrangements. Using Temporal Contrast Analysis we were able to detect two distinct dynamical components present during foam aging: spontaneous and intermittent, avalanche-like events and continuous, flow-like rearrangements in the foam structure. We were able to measure these contributions separately from the intrinsic statistical noise contribution, and thereby independently analyze the decay of each dynamical component during foam aging process.

We have engineered an antiferromagnetic domain wall by utilizing a magnetic frustration effect of a thin iron cap layer deposited on a chromium film. Through lithography and wet etching we selectively remove areas of the Fe cap layer to form a patterned ferromagnetic mask over the Cr film. Removing the Fe locally removes magnetic frustration in user-defined regions of the Cr film. We present x-ray microdiffraction microscopy results confirming the formation of a 90{\deg} spin-density wave propagation domain wall in Cr. This domain wall nucleates at the boundary defined by our Fe mask., Comment: submitted to APL

A two dimensional crystalline layer is found at the surface of the liquid eutectic Au$_{82}$Si$_{18}$ alloy above its melting point $T_M=359 ^{\circ}$C. Underlying this crystalline layer we find a layered structure, 6-7 atomic layers thick. This surface layer undergoes a first-order solid-solid phase transition occurring at $371 ^{\circ}$C. The crystalline phase observed for T$>$371 $^{\circ}$C is stable up to at least 430 $^{\circ}$C. Grazing Incidence X-ray Diffraction data at T$>$371 $^{\circ}$C imply lateral order comprising two coexisting phases of different oblique unit cells, in stark contrast with the single phase with a rectangular unit cell found for low-temperature crystalline phase $359 ^{\circ}$C$

X-ray reflectivity studies reveal atomic-level surface-segregation at the free surface of the eutectic Au71Sn29 liquid alloy. The surface-segregation extends up to three layers, in which the top layer is almost a pure monolayer of Sn, the second layer is almost a pure monolayer of Au and the third layer appears to be slightly enhanced in Au. Although the surface-segregation concentration profiles can be qualitatively accounted for by the theories of Defay-Prigogine and Strohl-King, they cannot satisfactorily account for the measured surface tension. PACS numbers: 61.20.-p, 61.10.-i, 68.03.-g, Comment: This paper will appear in Phys.RevB, 2007

X-ray measurements reveal a crystalline monolayer at the surface of the eutectic liquid Au_{82}Si_{18}, at temperatures above the alloy's melting point. Surface-induced atomic layering, the hallmark of liquid metals, is also found below the crystalline monolayer. The layering depth, however, is threefold greater than that of all liquid metals studied to date. The crystallinity of the surface monolayer is notable, considering that AuSi does not form stable bulk crystalline phases at any concentration and temperature and that no crystalline surface phase has been detected thus far in any pure liquid metal or nondilute alloy. These results are discussed in relation to recently suggested models of amorphous alloys., Comment: 12 pages, 3 figures, published in Science (2006)

The controlled self-assembly of thiol stabilized gold nanocrystals in a mediating solvent and confined within mesoporous alumina was probed in situ with small angle x-ray scattering. The evolution of the self-assembly process was controlled reversibly via regulated changes in the amount of solvent condensed from an undersaturated vapor. Analysis indicated that the nanoparticles self-assembled into cylindrical monolayers within the porous template. Nanoparticle nearest-neighbor separation within the monolayer increased and the ordering decreased with the controlled addition of solvent. The process was reversible with the removal of solvent. Isotropic clusters of nanoparticles were also observed to form temporarily during desorption of the liquid solvent and disappeared upon complete removal of liquid. Measurements of the absorption and desorption of the solvent showed strong hysteresis upon thermal cycling. In addition, the capillary filling transition for the solvent in the nanoparticle-doped pores was shifted to larger chemical potential, relative to the liquid/vapor coexistence, by a factor of 4 as compared to the expected value for the same system without nanoparticles., Comment: 9 pages, 9 figures, appeared in Phys. Rev. B

Resonant x-ray reflectivity of the surface of the liquid phase of the Bi$_{43}$Sn$_{57}$ eutectic alloy reveals atomic-scale demixing extending over three near-surface atomic layers. Due to the absence of underlying atomic lattice which typically defines adsorption in crystalline alloys, studies of adsorption in liquid alloys provide unique insight on interatomic interactions at the surface. The observed composition modulation could be accounted for quantitatively by the Defay-Prigogine and Strohl-King multilayer extensions of the single-layer Gibbs model, revealing a near-surface domination of the attractive Bi-Sn interaction over the entropy., Comment: 4 pages (two-column), 3 figures, 1 table; Added a figure, updated references, discussion; accepted at Phys. Rev. Lett

We present the first resonant x-ray reflectivity measurements from a liquid surface. The surface structure of the liquid Hg-Au alloy system just beyond the solubility limit of 0.14at% Au in Hg had previously been shown to exhibit a unique surface phase characterized by a low-density surface region with a complicated temperature dependence. In this paper we present reflectivity measurements near the Au LIII edge, for 0.2at% Au in Hg at room temperature. The data are consistent with a concentration of Au in the surface region that can be no larger than about 30at%. These results rule out previous suggestions that pure Au layers segregate at the alloy surface., Comment: 6 pages, 4 figures, published in Materials Science V Vol. 590

Surface sensitive x-ray scattering techniques with atomic scale resolution are employed to investigate the microscopic structure of the surface of three classes of liquid binary alloys: (i) Surface segregation in partly miscible binary alloys as predicted by the Gibbs adsorption rule is investigated for Ga-In. The first layer consists of a supercooled In monolayer and the bulk composition is reached after about two atomic diameters. (ii) The Ga-Bi system displays a wetting transition at a characteristic temperature T_w~220 C. The transition from a Bi monolayer on Ga below T_w to a thick Bi-rich wetting film above T_w is studied. (iii) The effect of attractive interactions between the two components of a binary alloy on the surface structure is investigated for two Hg-Au alloys., Comment: 20 pages, 6 figures, published in Ber. Bunsenges. Phys. Chem

Measurements of the surface x-ray scattering from several pure liquid metals (Hg, Ga, and In) and from three alloys (Ga-Bi, Bi-In, and K-Na) with different heteroatomic chemical interactions in the bulk phase are reviewed. Surface-induced layering is found for each elemental liquid metal. The surface structure of the K-Na alloy resembles that of an elemental liquid metal. Bi-In displays pair formation at the surface. Surface segregation and a wetting film are found for Ga-Bi., Comment: 10 pages, 3 fig, published in Journal of Physics: Condensed Matter

We report an x-ray scattering study of the microscopic structure of the surface of a liquid alkali metal. The bulk liquid structure factor of the eutectic K67Na33 alloy is characteristic of an ideal mixture, and so shares the properties of an elemental liquid alkali metal. Analysis of off-specular diffuse scattering and specular x-ray reflectivity shows that the surface roughness of the K-Na alloy follows simple capillary wave behavior with a surface structure factor indicative of surface induced layering. Comparison of thelow-angle tail of the K67Na33 surface structure factor with the one measured for liquid Ga and In previously suggests that layering is less pronounced in alkali metals. Controlled exposure of the liquid to H2 and O2 gas does not affect the surface structure, indicating that oxide and hydride are not stable at the liquid surface under these experimental conditions., Comment: 12 pages, 3 figures, published in Phys. Rev. B

Resonant x-ray reflectivity measurements from the surface of liquid Bi22In78 find only a modest surface Bi enhancement, with 35 atomic % Bi in the first atomic layer. This is in contrast to the Gibbs adsorption in all liquid alloys studied to date, which show surface segregation of a complete monolayer of the low surface tension component. This suggests that surface adsorption in Bi-In is dominated by attractive interactions that increase the number of Bi-In neighbors at the surface. These are the first measurements in which resonant x-ray scattering has been used to quantify compositional changes induced at a liquid alloy surface., Comment: 11 pages, 2 figures, 2 tables, published in Phys. Rev. Lett

Over the past two decades synchrotron facilities dedicated to the generation of x-rays for study of atoms, molecules and condensed matter have proliferated all over the world. As a result of the special properties of x-rays produced by these machines, there has been an enormous growth in the experimental possibilities. In this work we will demonstrate how these special properties can be used to carry out hitherto impossible measurements of the Angstrom level structure of the free surfaces of liquids. We demonstrate that surface structure of liquids is often different from that of the bulk. A large part of this thesis is devoted to surface-induced atomic or molecular layering phenomenon in metallic and dielectric liquids. In Chapters 1 through 10 we describe surface features of high-surface tension metals (Ga, In, Hg, Sn), as well as alkali metals (K, KNa) and water. The second part of the thesis (Chapters 11 through 16) is devoted to surface of binary metallic alloys (GaIn, HgAu, KNa, BiIn and GaBi), investigating a wide range of surface phenomena such as Gibbs adsorption and the tetra-point nanoscale wetting., Comment: Ph.D. Thesis, 388 pages, 84 figures, 7 tables; Physics Department, Harvard University (2004)

X-ray reflectivity measurements on the free surface of liquid Sn are presented. They exhibit the high-angle peak, indicative of surface-induced layering, also found for other pure liquid metals (Hg, Ga and In). However, a low-angle peak, not hitherto observed for any pure liquid metal, is also found, indicating the presence of a high-density surface layer. Fluorescence and resonant reflectivity measurements rule out the assignment of this layer to surface-segregation of impurities. The reflectivity is modelled well by a 10% contraction of the spacing between the first and second atomic surface layers, relative to that of subsequent layers. Possible reasons for this are discussed., Comment: 8 pages, 9 figures; to be submitted to Phys. Rev. B; updated references, expanded discussion

A continuous surface wetting transition, pinned to a solid/liquid/liquid/vapor tetra coexistence point, is studied by x-ray reflectivity in liquid Ga-Bi binary alloys. The short-range surface potential is determined from the measured temperature evolution of the wetting film. The thermal fluctuations are shown to be insufficient to induce a noticeable breakdown of mean-field behavior, expected in short-range-interacting systems due to their $d_u=3$ upper critical dimensionality., Comment: 4 pages (RevTeX 4), 3 eps figures, submitted to Physical Review Letters