Structural Changes during the Growth of Atomically Precise Metal Oxido Nanoclusters from Combined Pair Distribution Function and Small-Angle X-ray Scattering Analysis.

The combination of in situ pair distribution function (PDF) analysis and small-angle X-ray scattering (SAXS) enables analysis of the formation mechanism of metal oxido nanoclusters and cluster-solvent interactions as they take place. Herein, we demonstrate the method for the formation of clusters with a [Bi38 O45 ] core. Upon dissolution of crystalline [Bi6 O5 (OH)3 (NO3 )5 ]⋅3 H2 O in DMSO, an intermediate rapidly forms, which slowly grows to stable [Bi38 O45 ] clusters. To identify the intermediate, we developed an automated modeling method, where smaller [Bix Oy ] structures based on the [Bi38 O45 ] framework are tested against the data. [Bi22 O26 ] was identified as the main intermediate species, illustrating how combined PDF and SAXS analysis is a powerful tool to gain insight into nucleation on an atomic scale. PDF also provides information on the interaction between nanoclusters and solvent, which is shown to depend on the nature of the ligands on the cluster surface.

Complex imaging of phase domains by deep neural networks.

The reconstruction of a single-particle image from the modulus of its Fourier transform, by phase-retrieval methods, has been extensively applied in X-ray structural science. Particularly for strong-phase objects, such as the phase domains found inside crystals by Bragg coherent diffraction imaging (BCDI), conventional iteration methods are time consuming and sensitive to their initial guess because of their iterative nature. Here, a deep-neural-network model is presented which gives a fast and accurate estimate of the complex single-particle image in the form of a universal approximator learned from synthetic data. A way to combine the deep-neural-network model with conventional iterative methods is then presented to refine the accuracy of the reconstructed results from the proposed deep-neural-network model. Improved convergence is also demonstrated with experimental BCDI data.

Atomic resolution tracking of nerve-agent simulant decomposition and host metal-organic framework response in real space.

Gas capture and sequestration are valuable properties of metal-organic frameworks (MOFs) driving tremendous interest in their use as filtration materials for chemical warfare agents. Recently, the Zr-based MOF UiO-67 was shown to effectively adsorb and decompose the nerve-agent simulant, dimethyl methylphosphonate (DMMP). Understanding mechanisms of MOF-agent interaction is challenging due to the need to distinguish between the roles of the MOF framework and its particular sites for the activation and sequestration process. Here, we demonstrate the quantitative tracking of both framework and binding component structures using in situ X-ray total scattering measurements of UiO-67 under DMMP exposure, pair distribution function analysis, and theoretical calculations. The sorption and desorption of DMMP within the pores, association with linker-deficient Zr6 cores, and decomposition to irreversibly bound methyl methylphosphonate were directly observed and analyzed with atomic resolution.

sasPDF: pair distribution function analysis of nanoparticle assemblies from small-angle scattering data.

sasPDF, a method for characterizing the structure of nanoparticle assemblies (NPAs), is presented. The method is an extension of the atomic pair distribution function (PDF) analysis to the small-angle scattering (SAS) regime. The PDFgetS3 software package for computing the PDF from SAS data is also presented. An application of the sasPDF method to characterize structures of representative NPA samples with different levels of structural order is then demonstrated. The sasPDF method quantitatively yields information such as structure, disorder and crystallite sizes of ordered NPA samples. The method was also used to successfully model the data from a disordered NPA sample. The sasPDF method offers the possibility of more quantitative characterizations of NPA structures for a wide class of samples.

Structure-mining: screening structure models by automated fitting to the atomic pair distribution function over large numbers of models.

A new approach is presented to obtain candidate structures from atomic pair distribution function (PDF) data in a highly automated way. It fetches, from web-based structural databases, all the structures meeting the experimenter's search criteria and performs structure refinements on them without human intervention. It supports both X-ray and neutron PDFs. Tests on various material systems show the effectiveness and robustness of the algorithm in finding the correct atomic crystal structure. It works on crystalline and nanocrystalline materials including complex oxide nanoparticles and nanowires, low-symmetry and locally distorted structures, and complicated doped and magnetic materials. This approach could greatly reduce the traditional structure searching work and enable the possibility of high-throughput real-time auto-analysis PDF experiments in the future.

Ultrafast x-ray diffraction study of melt-front dynamics in polycrystalline thin films.

Melting is a fundamental process of matter that is still not fully understood at the microscopic level. Here, we use time-resolved x-ray diffraction to examine the ultrafast melting of polycrystalline gold thin films using an optical laser pump followed by a delayed hard x-ray probe pulse. We observe the formation of an intermediate new diffraction peak, which we attribute to material trapped between the solid and melted states, that forms 50 ps after laser excitation and persists beyond 500 ps. The peak width grows rapidly for 50 ps and then narrows distinctly at longer time scales. We attribute this to a melting band originating from the grain boundaries and propagating into the grains. Our observation of this intermediate state has implications for the use of ultrafast lasers for ablation during pulsed laser deposition.

Cluster-mining: an approach for determining core structures of metallic nanoparticles from atomic pair distribution function data.

A novel approach for finding and evaluating structural models of small metallic nanoparticles is presented. Rather than fitting a single model with many degrees of freedom, libraries of clusters from multiple structural motifs are built algorithmically and individually refined against experimental pair distribution functions. Each cluster fit is highly constrained. The approach, called cluster-mining, returns all candidate structure models that are consistent with the data as measured by a goodness of fit. It is highly automated, easy to use, and yields models that are more physically realistic and result in better agreement to the data than models based on cubic close-packed crystallographic cores, often reported in the literature for metallic nanoparticles.

Polymorphism in magic-sized Au144(SR)60 clusters.

Ultra-small, magic-sized metal nanoclusters represent an important new class of materials with properties between molecules and particles. However, their small size challenges the conventional methods for structure characterization. Here we present the structure of ultra-stable Au144(SR)60 magic-sized nanoclusters obtained from atomic pair distribution function analysis of X-ray powder diffraction data. The study reveals structural polymorphism in these archetypal nanoclusters. In addition to confirming the theoretically predicted icosahedral-cored cluster, we also find samples with a truncated decahedral core structure, with some samples exhibiting a coexistence of both cluster structures. Although the clusters are monodisperse in size, structural diversity is apparent. The discovery of polymorphism may open up a new dimension in nanoscale engineering.

Towards solution and refinement of organic crystal structures by fitting to the atomic pair distribution function.

A method towards the solution and refinement of organic crystal structures by fitting to the atomic pair distribution function (PDF) is developed. Approximate lattice parameters and molecular geometry must be given as input. The molecule is generally treated as a rigid body. The positions and orientations of the molecules inside the unit cell are optimized starting from random values. The PDF is obtained from carefully measured X-ray powder diffraction data. The method resembles `real-space' methods for structure solution from powder data, but works with PDF data instead of the diffraction pattern itself. As such it may be used in situations where the organic compounds are not long-range-ordered, are poorly crystalline, or nanocrystalline. The procedure was applied to solve and refine the crystal structures of quinacridone (ß phase), naphthalene and allopurinol. In the case of allopurinol it was even possible to successfully solve and refine the structure in P1 with four independent molecules. As an example of a flexible molecule, the crystal structure of paracetamol was refined using restraints for bond lengths, bond angles and selected torsion angles. In all cases, the resulting structures are in excellent agreement with structures from single-crystal data.

Complex modeling: a strategy and software program for combining multiple information sources to solve ill posed structure and nanostructure inverse problems.

A strategy is described for regularizing ill posed structure and nanostructure scattering inverse problems (i.e. structure solution) from complex material structures. This paper describes both the philosophy and strategy of the approach, and a software implementation, DiffPy Complex Modeling Infrastructure (DiffPy-CMI).

Atomic structures and gram scale synthesis of three tetrahedral quantum dots.

Luminescent semiconducting quantum dots (QDs) are central to emerging technologies that range from tissue imaging to solid-state lighting. However, existing samples are heterogeneous, which has prevented atomic-resolution determination of their structures and obscured the relationship between their atomic and electronic structures. Here we report the synthesis, isolation, and structural characterization of three cadmium selenide QDs with uniform compositions (Cd35Se20(X)30(L)30, Cd56Se35(X)42(L)42, Cd84Se56(X)56(L)56; X = O2CPh, L = H2N-C4H9). Their UV-absorption spectra show a lowest energy electronic transition that decreases in energy (3.54 eV, 3.26 eV, 3.04 eV) and sharpens as the size of the QD increases (fwhm = 207 meV, 145 meV, 115 meV). The photoluminescence spectra of all three QDs are broad with large Stokes shifts characteristic of trap-luminescence. Using a combination of single-crystal X-ray diffraction and atomic pair distribution function analysis, we determine the structures of their inorganic cores, revealing a series of pyramidal nanostuctures with cadmium terminated {111} facets. Theoretical and experimental studies on these materials will open the door to a deeper fundamental understanding of structure-property relationships in quantum-confined semiconductors.

Revealing the mechanisms behind SnO2 nanoparticle formation and growth during hydrothermal synthesis: an in situ total scattering study.

The formation and growth mechanisms in the hydrothermal synthesis of SnO(2) nanoparticles from aqueous solutions of SnCl(4)·5H(2)O have been elucidated by means of in situ X-ray total scattering (PDF) measurements. The analysis of the data reveals that when the tin(IV) chloride precursor is dissolved, chloride ions and water coordinate octahedrally to tin(IV), forming aquachlorotin(IV) complexes of the form [SnCl(x)(H(2)O)(6-x)]((4-x)+) as well as hexaaquatin(IV) complexes [Sn(H(2)O)(6-y)(OH)(y)]((4-y)+). Upon heating, ellipsoidal SnO(2) nanoparticles are formed uniquely from hexaaquatin(IV). The nanoparticle size and morphology (aspect ratio) are dependent on both the reaction temperature and the precursor concentration, and particles as small as ~2 nm can be synthesized. Analysis of the growth curves shows that Ostwald ripening only takes place above 200 °C, and in general the growth is limited by diffusion of precursor species to the growing particle. The c-parameter in the tetragonal lattice is observed to expand up to 0.5% for particle sizes down to 2-3 nm as compared to the bulk value. SnO(2) nanoparticles below 3-4 nm do not form in the bulk rutile structure, but as an orthorhombic structural modification, which previously has only been reported at pressures above 5 GPa. Thus, adjustment of the synthesis temperature and precursor concentration not only allows control over nanoparticle size and morphology but also the structure.

Tuning the Surface Structure and Optical Properties of CdSe Clusters Using Coordination Chemistry.

A series of nonstoichiometric CdSe clusters with lowest energy electronic absorptions between 409 - 420 nm has been prepared from cadmium 1-naphthoate, 2-naphthoate, 4-thiomethyl-1-naphthaote, and 1-naphthalene thiolate complexes and diphenylphosphine selenide (DPPSe). Pair distribution function analysis of X-ray diffraction data, ligand exchange experiments, and NMR molecular weight analyses suggest the nanocrystal core changes minimally among these clusters despite significant changes to their absorption and luminescence spectra. Photoluminescence excitation spectra obtained at 77 K reveal an energy transfer process between the surface-trapped excited state and the naphthalene-containing ligands that leads to ligand phosphorescence. A Dexter energy transfer mechanism is proposed to explain the observation of ligand phosphorescence on excitation of the cluster. These compounds demonstrate that cluster absorption and trap luminescence can be controlled with surface coordination chemistry.

Relationship between local structure and relaxor behavior in perovskite oxides.

Despite intensive investigations over the past five decades, the microscopic origins of the fascinating dielectric properties of ABO3 relaxor ferroelectrics are currently poorly understood. Here, we show that the frequency dispersion that is the hallmark of relaxor behavior is quantitatively related to the crystal chemical characteristics of the solid solution. Density functional theory is used in conjunction with experimental determination of cation arrangement to identify the 0 K structural motifs. These are then used to parametrize a simple phenomenological Landau theory that predicts the universal dependence of frequency dispersion on the solid solution cation arrangement and off-center cation displacements.