Neutron Instruments for Research in Coordination Chemistry.

Neutron diffraction and spectroscopy offer unique insight into structures and properties of solids and molecular materials. All neutron instruments located at the various neutron sources are distinct, even if their designs are based on similar principles, and thus, they are usually less familiar to the community than commercial X-ray diffractometers and optical spectrometers. Major neutron instruments in the USA, which are open to scientists around the world, and examples of their use in coordination chemistry research are presented here, along with a list of similar instruments at main neutron facilities in other countries. The reader may easily and quickly find from this minireview an appropriate neutron instrument for research. The instruments include single-crystal and powder diffractometers to determine structures, inelastic neutron scattering (INS) spectrometers to probe magnetic and vibrational excitations, and quasielastic neutron scattering (QENS) spectrometers to study molecular dynamics such as methyl rotation on ligands. Key and unique features of the diffraction and neutron spectroscopy that are relevant to inorganic chemistry are reviewed.

Benchmark Crystal Structure of Defect-Free Spinel ZnFe2O4.

Accurate structural models are of paramount importance for elucidating structure-property relationships in functional materials. Spinels (AB2O4) form a highly important family of materials with complex crystal structures, and subtle structural details have a critical bearing on understanding their physical properties. In some spinels, the space group symmetry is debated, and in general, point defects such as cation inversion and interstitials add complexity. Most studies of spinels concern powder materials, and this challenges deep structural characterization. In fact, most published spinel structures have dubious atomic displacement parameters (ADPs), which is a typical sign of problematic structural description in the refinement of diffraction data. Here, we use various X-ray and neutron diffraction techniques to establish a benchmark crystal structure for the essentially defect-free spinel ferrite ZnFe2O4, which is a widely studied frustrated magnet. It is shown that the appearance of Fd3̅m forbidden reflections in the ZnFe2O4 single-crystal neutron diffraction data is an artifact of multiple scattering rather than the loss of inversion symmetry. We then provide benchmark ADPs and demonstrate how strongly these parameters affect the refined cation inversion. The ADPs reported here may be used as reference data to test the soundness of refined structural models, possibly to constrain those based on suboptimal data quality, and thereby provide a more accurate fundamental understanding of the structure-property relationship in spinel-type materials.

Otoliths of sub-adult Lake Sturgeon Acipenser fulvescens contain aragonite and vaterite calcium carbonate polymorphs.

In this study we quantified the percent CaCO3 polymorph composition in otoliths of larval and juvenile Lake Sturgeon Acipenser fulvescens via X-ray microdiffraction. Sagittal otoliths of sub-adults were primarily composed of aragonite (> 90%) while the lapilli otoliths were 100% vaterite. This is the first time the presence of aragonite in otoliths has been reported in an acipenseriform and is surprising given that the ability to form aragonite otoliths was not thought to have evolved until the separation of teleost and holostean species from other Actinopterygian fishes (e.g., sturgeon, paddlefish, gar).

(+)-Cedrol hemihydrate: a natural product derived from drying eastern red cedar (Juniperus virginiana) wood.

Cedrol-like compounds are of pharmacological interest due to their diverse range of medicinal effects and are used globally in traditional medicines and cosmetics. Many cedrol tautomers are known from molecular studies but few have been studied in crystalline form by X-ray diffraction. Acicular white crystals collected from the wood of eastern red cedar (Juniperus virginiana) are determined to be (+)-cedrol hemihydrate, namely, (1S,2R,5S,7R,8R)-2,6,6,8-tetramethyltricyclo[5.3.1.01,5]undecan-8-ol hemihydrate, C15H26O·0.5H2O, a novel packing of two unique cedrol molecules (Z' = 2) with a single water molecule [space group P212121; a = 6.1956 (1), b = 14.5363 (1), and c = 30.9294 (4) Å]. The hydrogen bonding forms a one-dimensional spiral chain running along the a axis, following the chirality of the cedrol molecule, through hydrogen-bonding interactions with a right-handed helical configuration in graph-set notation Δ-C33(6) > a > c > b. The crystal packing and symmetry are different from crystalline isocedrol due to the different hydrogen-bonding geometry.

Giant Modulation of Refractive Index from Picoscale Atomic Displacements.

It is shown that structural disorder-in the form of anisotropic, picoscale atomic displacements-modulates the refractive index tensor and results in the giant optical anisotropy observed in BaTiS3, a quasi-1D hexagonal chalcogenide. Single-crystal X-ray diffraction studies reveal the presence of antipolar displacements of Ti atoms within adjacent TiS6 chains along the c-axis, and threefold degenerate Ti displacements in the a-b plane. 47/49Ti solid-state NMR provides additional evidence for those Ti displacements in the form of a three-horned NMR lineshape resulting from a low symmetry local environment around Ti atoms. Scanning transmission electron microscopy is used to directly observe the globally disordered Ti a-b plane displacements and find them to be ordered locally over a few unit cells. First-principles calculations show that the Ti a-b plane displacements selectively reduce the refractive index along the ab-plane, while having minimal impact on the refractive index along the chain direction, thus resulting in a giant enhancement in the optical anisotropy. By showing a strong connection between structural disorder with picoscale displacements and the optical response in BaTiS3, this study opens a pathway for designing optical materials with high refractive index and functionalities such as large optical anisotropy and nonlinearity.

The IMAGINE instrument: first neutron protein structure and new capabilities for neutron macromolecular crystallography.

The first high-resolution neutron protein structure of perdeuterated rubredoxin from Pyrococcus furiosus (PfRd) determined using the new IMAGINE macromolecular neutron crystallography instrument at the Oak Ridge National Laboratory is reported. Neutron diffraction data extending to 1.65 Šresolution were collected from a relatively small 0.7 mm(3) PfRd crystal using 2.5 d (60 h) of beam time. The refined structure contains 371 out of 391, or 95%, of the D atoms of the protein and 58 solvent molecules. The IMAGINE instrument is designed to provide neutron data at or near atomic resolution (1.5 Å) from crystals with volume <1.0 mm(3) and with unit-cell edges <100 Å. Beamline features include novel elliptical focusing mirrors that deliver neutrons into a 2.0 × 3.2 mm focal spot at the sample position with full-width vertical and horizontal divergences of 0.5 and 0.6°, respectively. Variable short- and long-wavelength cutoff optics provide automated exchange between multiple-wavelength configurations (λmin = 2.0, 2.8, 3.3 Što λmax = 3.0, 4.0, 4.5, ∼20 Å). These optics produce a more than 20-fold increase in the flux density at the sample and should help to enable more routine collection of high-resolution data from submillimetre-cubed crystals. Notably, the crystal used to collect these PfRd data was 5-10 times smaller than those previously reported.

Direct Visualization of Magnetic Correlations in Frustrated Spinel ZnFe2 O4.

Magnetic materials with the spinel structure (A2+ B3+ 2 O4 ) form the core of numerous magnetic devices, and ZnFe2 O4 constitutes a peculiar example where the nature of the magnetism is still unresolved. Susceptibility measurements revealed a cusp around Tc  = 13 K resembling an antiferromagnetic transition, despite the positive Curie-Weiss temperature determined to be ΘCW  = 102.8(1) K. Bifurcation of field-cooled and zero-field-cooled data below Tc in conjunction with a frequency dependence of the peak position and a non-zero imaginary component below Tc shows it is in fact associated with a spin-glass transition. Highly structured magnetic diffuse neutron scattering from single crystals develops between 50 K and 25 K revealing the presence of magnetic disorder which is correlated in nature. Here, the 3D-mΔPDF method is used to visualize the local magnetic ordering preferences, and ferromagnetic nearest-neighbor and antiferromagnetic third nearest-neighbor correlations are shown to be dominant. Their temperature dependence is extraordinary with some flipping in sign and a strongly varying correlation length. The correlations can be explained by orbital interaction mechanisms for the magnetic pathways and a preferred spin cluster. This study demonstrates the power of the 3D-mΔPDF method in visualizing complex quantum phenomena thereby providing a way to obtain an atomic-scale understanding of magnetic frustration.

Colossal Optical Anisotropy from Atomic-Scale Modulations.

Materials with large birefringence (Δn, where n is the refractive index) are sought after for polarization control (e.g., in wave plates, polarizing beam splitters, etc.), nonlinear optics, micromanipulation, and as a platform for unconventional light-matter coupling, such as hyperbolic phonon polaritons. Layered 2D materials can feature some of the largest optical anisotropy; however, their use in most optical systems is limited because their optical axis is out of the plane of the layers and the layers are weakly attached. This work demonstrates that a bulk crystal with subtle periodic modulations in its structure-Sr9/8 TiS3 -is transparent and positive-uniaxial, with extraordinary index ne = 4.5 and ordinary index no = 2.4 in the mid- to far-infrared. The excess Sr, compared to stoichiometric SrTiS3 , results in the formation of TiS6 trigonal-prismatic units that break the chains of face-sharing TiS6 octahedra in SrTiS3 into periodic blocks of five TiS6 octahedral units. The additional electrons introduced by the excess Sr form highly oriented electron clouds, which selectively boost the extraordinary index ne and result in record birefringence (Δn > 2.1 with low loss). The connection between subtle structural modulations and large changes in refractive index suggests new categories of anisotropic materials and also tunable optical materials with large refractive-index modulation.

Charge Density Wave Order and Electronic Phase Transitions in a Dilute d-Band Semiconductor.

As one of the most fundamental physical phenomena, charge density wave (CDW) order predominantly occurs in metallic systems such as quasi-1D metals, doped cuprates, and transition metal dichalcogenides, where it is well understood in terms of Fermi surface nesting and electron-phonon coupling mechanisms. On the other hand, CDW phenomena in semiconducting systems, particularly at the low carrier concentration limit, are less common and feature intricate characteristics, which often necessitate the exploration of novel mechanisms, such as electron-hole coupling or Mott physics, to explain. In this study, an approach combining electrical transport, synchrotron X-ray diffraction, and density-functional theory calculations is used to investigate CDW order and a series of hysteretic phase transitions in a dilute d-band semiconductor, BaTiS3 . These experimental and theoretical findings suggest that the observed CDW order and phase transitions in BaTiS3 may be attributed to both electron-phonon coupling and non-negligible electron-electron interactions in the system. This work highlights BaTiS3 as a unique platform to explore CDW physics and novel electronic phases in the dilute filling limit and opens new opportunities for developing novel electronic devices.

Spin reorientation in TlFe1.6Se2 with complete vacancy ordering.

The relationship between vacancy ordering and magnetism in TlFe(1.6)Se(2) has been investigated via single crystal neutron diffraction, nuclear forward scattering, and transmission electron microscopy. The examination of chemically and structurally homogeneous crystals allows the true ground state to be revealed, which is characterized by Fe moments lying in the ab plane below 100 K. This is in sharp contrast to crystals containing regions of order and disorder, where a competition between c axis and ab plane orientations of the moments is observed. The properties of partially disordered TlFe(1.6)Se(2) are, therefore, not associated with solely the ordered or disordered regions. This contrasts the viewpoint that phase separation results in independent physical properties in intercalated iron selenides, suggesting a coupling between ordered and disordered regions may play an important role in the superconducting analogues.

Neutron diffraction study of the type I clathrate Ba8Al(x)Si(46-x): site occupancies, cage volumes, and the interaction between the guest and the host framework.

Samples with the type I clathrate structure and composition Ba(8)Al(x)Si(46-x), where x = 8, 10, 12, 14, and 15, were examined by neutron powder diffraction at 35 K. The clathrate type I structure contains Ba cations as guests in a framework derived from tetrahedrally coordinated Al/Si atoms. The framework is made up of five- and six-membered rings that form dodecahedral and tetrakaidecahedral cages. The change in distances between tetrahedral sites across the series is used to develop a model for the mixed Al/Si occupancy observed in the framework. The calculated volumes of the cages that contain the Ba atoms display a linear increase with increasing Al composition. In the smaller dodecahedral cages, the Ba atomic displacement parameter is symmetry constrained to be isotropic for all compositions. In the larger tetrakaidecahedral cages, the anisotropic atomic displacement of the Ba atom depends upon the composition: the displacement is perpendicular (x = 8) and parallel (x = 15) to the six-membered ring. This difference in direction of the displacement parameter is attributed to interaction with the Al in the framework and not to the size of the cage volume as x increases from 8 to 15. The influence of the site occupation of Al in the framework on displacement of the cation at the 6d site is demonstrated.

New family of cerium halide based materials: CeX3·ROH compounds containing planes, chains, and tetradecanuclear rings.

Six members of a new family of cerium-halide-based materials with promising scintillation behavior have been synthesized in single crystal form, and their crystal structures were determined. Specifically, these new compounds are [(CeCl(3))(7)(BuOH)(16)(H(2)O)(2)]·(BuOH)(2) (1), (CeBr(3))(14)(BuOH)(36) (2), [(CeCl(3))(7)(1-PrOH)(16)(H(2)O)(2)]·(1-PrOH)(2) (3), [(CeBr(3))(7)(1-PrOH)(18)]·(1-PrOH)(2) (4), [(CeCl(3))(6)(iBuOH)(15)]·(iBuOH)(2) (5), and CeCl(3)(sec-BuOH)(2)(H(2)O) (6). Additionally, the scintillation ability of compound 1 was established. The structures of these cerium-halide-based materials consist of catenated tetradecanuclear rings that arrange themselves into three distinct structural motifs which contain the largest lanthanide-based ring structures reported to date; the different motifs are obtained by involving specific alcohols during synthesis. Specifically, n-butanol and n-propanol lead to 1-D chains of tetradecanuclear rings, and iso-butanol leads to 2-D parquet-patterned sheets of rectangular tetradecanuclear rings, while sec-butanol results in a zigzag 1-D chain structure. One of the compounds, [(CeCl(3))(6)(iBuOH)(15)]·(iBuOH)(2), has been shown to scintillate with a light yield of up to 1920 photons/MeV, and due to the presence of protons, it should be capable of detecting high energy neutrons without the necessity of prior thermalization. Furthermore, it also appears to be the first cerium-based compound that scintillates in spite of the fact that water coordinates to two of the Ce(III) centers within the structure.

PIONEER, a high-resolution single-crystal polarized neutron diffractometer.

PIONEER is a high Q-resolution, single-crystal, polarized neutron diffractometer at the Second Target Station (STS), Oak Ridge National Laboratory. It will provide the unprecedented capability of measuring tiny crystals (0.001 mm3, i.e., x-ray diffraction size), ultra-thin films (10 nm thickness), and weak structural and magnetic transitions. PIONEER benefits from the increased peak brightness of STS cold-neutron sources and uses advanced Montel mirrors that are able to deliver a focused beam with a high brilliance transfer, a homogeneous profile, and a low background. Monte Carlo simulations suggest that the optimized instrument has a high theoretical peak brilliance of 2.9 × 1012 n cm-2 sr-1 Å-1 s-1 at 2.5 Å at the sample position, within a 5 × 5 mm2 region and a ±0.3° divergence range. The moderator-to-sample distance is 60 m, providing a nominal wavelength band of 4.3 Å with a wavelength resolution better than 0.2% in the wavelength range of 1.0-6.0 Å. PIONEER is capable of characterizing large-scale periodic structures up to 200 Å. With a sample-to-detector distance of 0.8 m, PIONEER accommodates various sample environments, including low/high temperature, high pressure, and high magnetic/electric field. A large cylindrical detector array (4.0 sr) with a radial collimator is planned to suppress the background scattering from sample environments. Bottom detector banks provide an additional 0.4 sr coverage or can be removed if needed to accommodate special sample environments. We present virtual experimental results to demonstrate the scientific performance of PIONEER in measuring tiny samples.

Quantifying fish otolith mineralogy for trace-element chemistry studies.

Otoliths are frequently used to infer environmental conditions or fish life history events based on trace-element concentrations. However, otoliths can be comprised of any one or combination of the three most common polymorphs of calcium carbonate-aragonite, calcite, and vaterite-which can affect the ecological interpretation of otolith trace-element results. Previous studies have reported heterogeneous calcium carbonate compositions between left and right otoliths but did not provide quantitative assessments of polymorph abundances. In this study, neutron diffraction and Raman spectroscopy were used to identify and quantify mineralogical compositions of Chinook salmon Oncorhynchus tshawytscha otolith pairs. We found mineralogical compositions frequently differed between otoliths in a pair and accurate calcium carbonate polymorph identification was rarely possible by visual inspection alone. The prevalence of multiple polymorphs in otoliths is not well-understood, and future research should focus on identifying otolith compositions and investigate how variations in mineralogy affect trace-element incorporation and potentially bias environmental interpretations.

rmc-discord: reverse Monte Carlo refinement of diffuse scattering and correlated disorder from single crystals.

A user-friendly program has been developed to analyze diffuse scattering from single crystals with the reverse Monte Carlo method. The approach allows for refinement of correlated disorder from atomistic supercells with magnetic or structural (occupational and/or displacive) disorder. The program is written in Python and optimized for performance and efficiency. Refinements of two user cases obtained with legacy neutron-scattering data demonstrate the effectiveness of the approach and the developed program. It is shown with bixbyite, a naturally occurring magnetic mineral, that the calculated three-dimensional spin-pair correlations are resolved with finer real-space resolution compared with the pair distribution function calculated directly from the reciprocal-space pattern. With the triangular lattice Ba3Co2O6(CO3)0.7, refinements of occupational and displacive disorder are combined to extract the one-dimensional intra-chain correlations of carbonate molecules that move toward neighboring vacant sites to accommodate strain induced by electrostatic interactions. The program is packaged with a graphical user interface and extensible to serve the needs of single-crystal diffractometer instruments that collect diffuse-scattering data.

Morphology and composition of Goldeye (Hiodontidae; Hiodon alosoides) otoliths.

We provide up-to-date morphological and compositional data on otoliths of the osteoglossomorph Goldeye (Hiodon alosoides). Using computed tomography (CT) X-ray, we documented the location of each of the three pairs of otoliths (lapilli, sagittae, and asterisci) in relation to the swim bladder, which extended forward in close proximity to the sagittae and asterisci. The lappili were the largest otoliths in terms of surface area and volume, but the sagittae were highly modified, appearing spiral in shape when viewed dorsally, with a surface area to volume ratio more than double that of the lapilli. Using scanning electron microscopy, the surface of each otolith was viewable in great detail, and small otoconia (~10.5 µm diameter) were observed on each, but were most numerous on the sagittae. On scanning electron micrographs, the sagittae appeared to be bi-lobed, with asymmetrical lobes each oriented in the same general direction. Using neutron and X-ray diffraction methods, we found three polymorphs of calcium carbonate crystals (aragonite, vaterite, and calcite), sometimes all within the same otolith. However, in general, lapilli and sagittae were composed predominately of aragonite whereas asterisci were composed chiefly of vaterite. With these results, we provide information on a unique species, whose inclusion in future studies would benefit our understanding of fish hearing, fish evolution, and fisheries ecology.

Influence of ontogenetic development, temperature, and pCO2 on otolith calcium carbonate polymorph composition in sturgeons.

Changes to calcium carbonate (CaCO3) biomineralization in aquatic organisms is among the many predicted effects of climate change. Because otolith (hearing/orientation structures in fish) CaCO3 precipitation and polymorph composition are controlled by genetic and environmental factors, climate change may be predicted to affect the phenotypic plasticity of otoliths. We examined precipitation of otolith polymorphs (aragonite, vaterite, calcite) during early life history in two species of sturgeon, Lake Sturgeon, (Acipenser fulvescens) and White Sturgeon (A. transmontanus), using quantitative X-ray microdiffraction. Both species showed similar fluctuations in otolith polymorphs with a significant shift in the proportions of vaterite and aragonite in sagittal otoliths coinciding with the transition to fully exogenous feeding. We also examined the effect of the environment on otolith morphology and polymorph composition during early life history in Lake Sturgeon larvae reared in varying temperature (16/22 °C) and pCO2 (1000/2500 µatm) environments for 5 months. Fish raised in elevated temperature had significantly increased otolith size and precipitation of large single calcite crystals. Interestingly, pCO2 had no statistically significant effect on size or polymorph composition of otoliths despite blood pH exhibiting a mild alkalosis, which is contrary to what has been observed in several studies on marine fishes. These results suggest climate change may influence otolith polymorph composition during early life history in Lake Sturgeon.

Piezoelectric domain walls in van der Waals antiferroelectric CuInP2Se6.

Polar van der Waals chalcogenophosphates exhibit unique properties, such as negative electrostriction and multi-well ferrielectricity, and enable combining dielectric and 2D electronic materials. Using low temperature piezoresponse force microscopy, we revealed coexistence of piezoelectric and non-piezoelectric phases in CuInP2Se6, forming unusual domain walls with enhanced piezoelectric response. From systematic imaging experiments we have inferred the formation of a partially polarized antiferroelectric state, with inclusions of structurally distinct ferrielectric domains enclosed by the corresponding phase boundaries. The assignment is strongly supported by optical spectroscopies and density-functional-theory calculations. Enhanced piezoresponse at the ferrielectric/antiferroelectric phase boundary and the ability to manipulate this entity with electric field on the nanoscale expand the existing phenomenology of functional domain walls. At the same time, phase-coexistence in chalcogenophosphates may lead to rational strategies for incorporation of ferroic functionality into van der Waals heterostructures, with stronger resilience toward detrimental size-effects.

Texture Analysis of Polycrystalline Vaterite Spherulites from Lake Sturgeon Otoliths.

Fish otoliths, or ear bones, are comprised of the CaCO3 polymorphs (aragonite, calcite and vaterite), which can occur either alone or in combination. The polymorph phase abundance in an otolith depends on, as yet, unexplained genetic and environmental factors. Most fish otoliths are comprised of the densest CaCO3 polymorph, aragonite. Sturgeon otoliths, on the other hand, contain significant amounts of the rare and the structurally enigmatic polymorph, vaterite. Sturgeon otoliths are frequently comprised of agglomerations of small microcrystalline vaterite spherulites (<300 µm in diameter), that range in shape from nearly perfect spheres to oblate spheroids. These spherulites are similar to the synthetic vaterite microspheres employed in laser trapping applications. Vaterite spherulites from both hatchery-reared (juvenile) and wild (adult) Lake Sturgeon exhibit extreme crystallographic texture as evidenced by X-ray diffraction patterns and their reconstructed pole-figures determined here. The vaterite crystallites making up the spherulites have excellent registry in both the axial and equatorial directions. Whether synthesized or natural, the texture manifested in these spherulites suggests that vaterite nucleates and grows similarly in vivo otolith formation as well as from laboratory synthesis. The uniaxial optical character of the vaterite spherulites, confirmed by these diffraction experiments and combined with their large birefringence, makes them well suited for laser trapping applications.

Model-free reconstruction of magnetic correlations in frustrated magnets.

Frustrated magnetic systems exhibit extraordinary physical properties, but quantification of their magnetic correlations poses a serious challenge to experiment and theory. Current insight into frustrated magnetic correlations relies on modelling techniques such as reverse Monte-Carlo methods, which require knowledge about the exact ordered atomic structure. Here, we present a method for direct reconstruction of magnetic correlations in frustrated magnets by three-dimensional difference pair distribution function analysis of neutron total scattering data. The methodology is applied to the disordered frustrated magnet bixbyite, (Mn1-x Fe x )2O3, which reveals nearest-neighbor antiferromagnetic correlations for the metal sites up to a range of approximately 15 Å. Importantly, this technique allows for magnetic correlations to be determined directly from the experimental data without any assumption about the atomic structure.