Search

We present observations of the four 2 Pi 3/2 J = 3/2 ground-rotational state transitions of the hydroxyl molecule (OH) along 107 lines of sight both in and out of the Galactic plane: 92 sets of observations from the Arecibo telescope and 15 sets of observations from the Australia Telescope Compact Array (ATCA). Our Arecibo observations included off-source pointings, allowing us to measure excitation temperature (Tex) and optical depth, while our ATCA observations give optical depth only. We perform Gaussian decomposition using the Automated Molecular Excitation Bayesian line-fitting Algorithm 'AMOEBA' (Petzler, Dawson, and Wardle 2021) fitting all four transitions simultaneously with shared centroid velocity and width. We identify 109 features across 38 sightlines (including 58 detections along 27 sightlines with excitation temperature measurements). While the main lines at 1665 and 1667 MHz tend to have similar excitation temperatures (median Tex(main) difference = 0.6 K, 84% show Tex(main) difference < 2 K), large differences in the 1612 and 1720 MHz satellite line excitation temperatures show that the gas is generally not in LTE. For a selection of sightlines we compare our OH features to associated (on-sky and in velocity) HI cold gas components (CNM) identified by Nguyen et al. (2019) and find no strong correlations. We speculate that this may indicate an effective decoupling of the molecular gas from the CNM once it accumulates., Accepted for publication to PASA. 41 pages, 27 figures

We present a comprehensive structural and magnetic characterization of the barlowite family of S = 1/2 kagomé magnets, Cu4(OH)6FX, where X = Cl, Br, or I. Through high-resolution synchrotron X-ray and neutron powder diffraction measurements, we reveal two sources of structural complexity within this family of materials, namely, compositional disorder of the halide species that occupy sites in between the kagomé layers and the positional disorder of the interlayer Cu2+ ions that persists well into the Pnma structural ground state. We demonstrate that understanding these inherent structural disorders is key as they correlate with the degree of partial order in the magnetic ground states of these quantum frustrated magnets.

Interpersonal synchrony (IS) is the temporal co-ordination of behavior during social interactions. IS acts as a social cue signifying affiliation, both when children witness IS between others and when they experience it themselves. However, it is unclear which temporal qualities of IS produce these effects, and why. We hypothesized that the simultaneity and temporal regularity of partners’ actions would each influence affiliation judgements, and that subjective perceptions of IS (‘togetherness’) would play a role in mediating these relations. In two online studies, children aged 4-11 years listened to a pair of children tapping together (witnessed IS; N=68) or themselves tapped with another child (experienced IS; N=63). Tapping partners were presented as real, but the sounds attributed to them were computer generated so that their temporal relations could be experimentally manipulated. The simultaneity and regularity of their tapping was systematically manipulated across trials. For witnessed IS, both the simultaneity and regularity of partners’ tapping significantly positively affected the perceived degree of affiliation between them. These effects were mediated by the perceived togetherness of the tapping. No affiliative effects of IS were found in the experienced IS condition. Our findings suggest that both the simultaneity and regularity of partners’ actions influence children’s affiliation judgements when witnessing IS, via elicited perceptions of togetherness. We conclude that temporal interdependence – which includes but is not limited to simultaneity of action – is responsible for inducing perceptions of affiliation during witnessed IS.

X-ray characterisation methods have undoubtedly enabled cutting-edge advances in all aspects of materials research. Despite the enormous breadth of information that can be extracted from these techniques, the challenge of radiation-induced sample change and damage remains prevalent. This is largely due to the emergence of modern, high-intensity X-ray source technologies and the growing potential to carry out more complex, longer duration

The flexibility of the zeolite Rho framework offers great potential for tunable molecular sieving. The fully copper‐exchanged form of Rho and mixed Cu,H‐ and Cu,Na‐forms have been prepared. EPR spectroscopy reveals that Cu2+ ions are present in the dehydrated forms and Rietveld refinement shows these prefer S6R sites, away from the d8r windows that control diffusion. Fully exchanged Cu‐Rho remains in an open form upon dehydration, the d8r windows remain nearly circular and the occupancy of window sites is low, so that it adsorbs CO2 rapidly at room temperature. Breakthrough tests with 10 % CO2/40 % CH4 mixtures show that Cu4.9‐Rho is able to produce pure methane, albeit with a relatively low capacity at this pCO2 due to the weak interaction of CO2 with Cu cations. This is in strong contrast to Na‐Rho, where cations in narrow elliptical window sites enable CO2 to be adsorbed with high selectivity and uptake but too slowly to enable the production of pure methane in similar breakthrough experiments. A series of Cu,Na‐Rho materials was prepared to improve uptake and selectivity compared to Cu‐Rho, and kinetics compared to Na‐Rho. Remarkably, Cu,Na‐Rho with >2 Cu cations per unit cell exhibited exsolution, due to the preference of Na cations for narrow S8R sites in distorted Rho and of Cu cations for S6R sites in the centric, open form of Rho. The exsolved Cu,Na‐Rho showed improved performance in CO2/CH4 breakthrough tests, producing pure CH4 with improved uptake and CO2/CH4 selectivity compared to that of Cu4.9‐Rho., Copper cations favour 6‐membered ring (6R) sites in dehydrated zeolite Rho, away from 8R windows that allow adsorption into lta cages. Exchange of Cu cations into Na‐Rho, in which Na cations occupy 8R gating sites between the lta cages, improves CO2 uptake kinetics, while retaining some Na cations enhances CO2/CH4 selectivity. Upon dehydration, Cu,Na‐Rho shows exsolution behaviour, because its framework can adopt distorted and undistorted forms that provide favourable coordination sites for Na and Cu cations, respectively.

X-ray characterisation methods have undoubtedly enabled cutting-edge advances in all aspects of materials research. Despite the enormous breadth of information that can be extracted from these techniques, the challenge of radiation-induced sample change and damage remains prevalent. This is largely due to the emergence of modern, high-intensity X-ray source technologies and growing potential to carry out more complex, longer duration in-situ or in-operando studies. The tunability of synchrotron beamlines enables the routine application of photon energy-dependent experiments. This work explores the structural stability of [Rh(COD)Cl]2, a widely used catalyst and precursor in the chemical industry, across a range of beamline parameters that target X-ray energies of 8 keV, 15 keV, 18 keV and 25 keV, on a powder X-ray diffraction synchrotron beamline at room temperature. Structural changes are discussed with respect to absorbed X-ray dose at each experimental setting associated with the respective photon energy. In addition, the X-ray radiation hardness of the catalyst is discussed, by utilising the diffraction data at the different energies to determine a dose limit, which is often considered in protein crystallography and typically overlooked in small molecule crystallography. This work not only gives fundamental insight into how damage manifests in this organometallic catalyst, but will encourage careful consideration of experimental X-ray parameters before conducting diffraction on similar radiation-sensitive organometallic materials., 20 pages, 7 figures

Mechanochemical synthesis has recently emerged as a scalable “green” approach for the preparation of MOFs, but current understanding of the underlying reaction mechanisms is limited. In this work, an investigation of the reaction pathway of the mechanochemical synthesis of MOF-74 from ZnO and 2,5-dihydroxyterephthalic acid (H4HDTA), using DMF as a liquid additive, is presented. The complex reaction pathway involves the formation of four short-lived intermediate phases, prior to the crystallization of MOF-74. The crystal structures of three of these intermediates have been determined using a combination of single-crystal and powder X-ray diffraction methods and are described here. The initial stages of the reaction are very fast, with a DMF solvate of H4HDTA forming after only 2 min of milling. This is followed by crystallization, after only 4 min of milling, of a triclinic one-dimensional coordination polymer, Zn(H2DHTA)(DMF)2(H2O)2, which converts into a monoclinic polymorph on additional milling. Highly crystalline MOF-74 appears after prolonged milling, for at least 70 min., The mechanochemical synthesis of MOF-74 from ZnO and 2,5-dihydroxyterephthalic acid, using DMF as a liquid additive, has been investigated. The reaction pathway of involves the formation of four short-lived intermediate phases prior to the crystallization of the final product, MOF-74.

The demand for xylenes is projected to increase over the coming decades. The separation of xylene isomers, particularly p- and m-xylenes, is vital for the production of numerous polymers and materials. However, current state-of-the-art separation is based upon fractional crystallisation at 220 K which is highly energy intensive. Here, we report the discrimination of xylene isomers via refinement of the pore size in a series of porous metal–organic frameworks, MFM-300, at sub-angstrom precision leading to the optimal kinetic separation of all three xylene isomers at room temperature. The exceptional performance of MFM-300 for xylene separation is confirmed by dynamic ternary breakthrough experiments. In-depth structural and vibrational investigations using synchrotron X-ray diffraction and terahertz spectroscopy define the underlying host–guest interactions that give rise to the observed selectivity (p-xylene < o-xylene < m-xylene) and separation factors of 4.6–18 for p- and m-xylenes., Separation of xylene isomers is essential for the production of a wide range of materials, but current separation methods are energy intensive. Here the authors report separation of the three xylene isomers at room temperature, via refinement of the pore size in a series of porous MOFs at sub-angstrom precision.

The authors thank the EPSRC for funding (Cation-controlled gating for selective gas adsorption over adaptable zeolites: EP/N032942/1, V.M.G., P.A.W.; EP/N033329/1, M.C.V. and S.B.; an NPIF Ph.D. scholarship for E.L.B.: EP/R512199/1). Small pore zeolites that show framework flexibility, such as merlinoite (topology type MER), possess high potential for the selective adsorption of small gas molecules including CO2. The CO2 adsorption properties of Na-, K- and Cs-exchanged forms of a merlinoite zeolite with Si/Al = 4.2 have been measured at 298 K and in situ PXRD used to follow their structural response to dehydration and CO2 uptake. The Na- and Cs- forms convert from a wide-pore to a narrow-pore form upon dehydration, while the K-form remains in the wide-pore form. The Na- and Cs-forms exhibit stepped CO2 adsorption isotherms, consistent with breathing behaviour and expansion from narrow- to wide-pore phases, whilst K6.2-MER remains in the wide-pore structure throughout. Synchrotron PXRD of the K- and Cs-forms reveals the effects of CO2 adsorption on the cation site distributions and the framework configuration. All cation forms of MER (4.2) show enhanced adsorption kinetics for Ar compared to those with lower Si/Al and the wide-pore structure of K6.2-MER (4.2) shows particularly rapid sorption for both Ar and CO2. Breakthrough curves over K6.2-MER(4.2) demonstrate good separation of CO2 from CH4 in flowing CO2/CH4 mixtures, even in pelletised form with an alumina binder. Postprint Postprint

Using new large area maps of the cold neutral medium (CNM) fraction, $f_{\rm CNM}$, we investigate the relationship between the CNM, the abundance of polycyclic aromatic hydrocarbons (PAHs), and the anomalous microwave emission (AME). We first present our $f_{\rm CNM}$ map based on full-sky HI4PI data, using a convolutional neural network to covert the spectroscopic HI data to $f_{\rm CNM}$. We demonstrate that $f_{\rm CNM}$ is strongly correlated with the fraction of dust in PAHs as estimated from mid- and far-infrared dust emission. In contrast, we find no correlation between $f_{\rm CNM}$ and the amount of AME per dust emission, nor between $f_{\rm CNM}$ and the AME peak frequency. These results suggest PAHs preferentially reside in cold, relatively dense gas, perhaps owing to enhanced destruction in more diffuse media. The lack of correlation between $f_{\rm CNM}$ and AME peak frequency is in tension with expectations from theoretical models positing different spectral energy distributions of AME in the cold versus warm neutral medium. We suggest that different PAH abundances and emission physics in different interstellar environments may explain the weaker than expected correlation between 12$\mu$m PAH emission and AME even if PAHs are the AME carriers., Comment: Submitted to ApJ. 12 pages, 4 figures, comments welcome

To achieve optimal performance in gas storage and delivery applications, metal-organic frameworks (MOFs) must combine high gravimetric and volumetric capacities. One potential route to balancing high pore volume with suitable crystal density is interpenetration, where identical nets sit within the void space of one another. Herein, we report an interpenetrated MIL-53 topology MOF, named GUF-1, where one-dimensional Sc(µ2-OH) chains are connected by 4,4’-(ethyne-1,2-diyl)dibenzoate linkers into a material that is an unusual example of an interpenetrated MOF with a rod-like secondary building unit. A combination of modulated self-assembly and grand canonical Monte Carlo simulations are used to optimise the porosity of GUF-1; H2 adsorption isotherms reveal a very high Qst for H2 of 7.6 kJ mol-1 and a working capacity of 41 g L-1 in a temperature-pressure swing system, which is comparable to benchmark MOFs. These results show that interpenetration is a viable route to high performance gas storage materials comprised of relatively simple building blocks.

We have complemented existing observations of HI absorption with new observations of HCO$^+$, C$_2$H, HCN, and HNC absorption from the Atacama Large Millimeter/submillimeter Array (ALMA) and the Northern Extended Millimeter Array (NOEMA) in the direction of 20 background radio continuum sources with $4^\circ \leq |b| \leq 81^\circ$ to constrain the atomic gas conditions that are suitable for the formation of diffuse molecular gas. We find that these molecular species form along sightlines where $A_V \gtrsim 0.25$, consistent with the threshold for the HI-to-H$_2$ transition at solar metallicity. Moreover, we find that molecular gas is associated only with structures that have an HI optical depth $> 0.1$, a spin temperature $< 80$ K, and a turbulent Mach number $\gtrsim 2$. We also identify a broad, faint component to the HCO$^+$ absorption in a majority of sightlines. Compared to the velocities where strong, narrow HCO$^+$ absorption is observed, the HI at these velocities has a lower cold neutral medium (CNM) fraction and negligible CO emission. The relative column densities and linewidths of the different molecular species observed here are similar to those observed in previous experiments over a range of Galactic latitudes, suggesting that gas in the solar neighborhood and gas in the Galactic plane are chemically similar. For a select sample of previously-observed sightlines, we show that the absorption line profiles of HCO$^+$, HCN, HNC, and C$_2$H are stable over periods of $\sim 3$ years and $\sim 25$ years, likely indicating that molecular gas structures in these directions are at least $\gtrsim 100$ AU in size, 31 pages, 12 figures, 8 tables. Accepted to ApJ

X-ray characterization techniques are invaluable for probing material characteristics and properties, and have been instrumental in discoveries across materials research. However, there is a current lack of understanding of how X-ray-induced effects manifest in small molecular crystals. This is of particular concern as new X-ray sources with ever-increasing brilliance are developed. In this paper, systematic studies of X-ray-matter interactions are reported on two industrially important catalysts, [Ir(COD)Cl]

We report the aperiodic titanate Ba10Y6Ti4O27 with a room‐temperature thermal conductivity that equals the lowest reported for an oxide. The structure is characterised by discontinuous occupancy modulation of each of the sites and can be considered as a quasicrystal. The resulting localisation of lattice vibrations suppresses phonon transport of heat. This new lead material for low‐thermal‐conductivity oxides is metastable and located within a quaternary phase field that has been previously explored. Its isolation thus requires a precisely defined synthetic protocol. The necessary narrowing of the search space for experimental investigation was achieved by evaluation of titanate crystal chemistry, prediction of unexplored structural motifs that would favour synthetically accessible new compositions, and assessment of their properties with machine‐learning models., Ba10Y6Ti4O27 has a complex aperiodic structure with the lowest thermal conductivity of any first‐transition‐series oxide. It is metastable, which makes it challenging to identify. Experimental exploration was focused sufficiently by structure prediction and property‐targeted machine learning to enable the isolation of this material (see picture), whose structural motifs provide new insight into the control of heat transport.

Li–N–H materials, particularly lithium amide and lithium imide, have been explored for use in a variety of energy storage applications in recent years. Compositional variation within the parent lithium imide, anti-fluorite crystal structure has been related to both its facile storage of hydrogen and impressive catalytic performance for the decomposition of ammonia. Here, we explore the controlled solid-state synthesis of Li–N–H solid-solution anti-fluorite structures ranging from amide-dominated (Li4/3(NH2)2/3(NH)1/3 or Li1.333NH1.667) through lithium imide to majority incorporation of lithium nitride–hydride (Li3.167(NH)0.416N0.584H0.584 or Li3.167NH). Formation of these solid solutions is demonstrated to cause significant changes to the thermal stability and ammonia reactivity of the samples, highlighting the potential use of compositional variation to control the properties of the material in gas storage and catalytic applications., A wide solid solution based on the lithium imide anti-fluorite structure is demonstrated and related to its energy storage functions.

X-ray characterization techniques are invaluable for probing material characteristics and properties, and have been instrumental in discoveries across materials research. However, there is a current lack of understanding of how X-ray-induced effects manifest in small molecular crystals. This is of particular concern as new X-ray sources with ever-increasing brilliance are developed. In this paper, systematic studies of X-ray-matter interactions are reported on two industrially important catalysts, [Ir(COD)Cl]2 and [Rh(COD)Cl]2, exposed to radiation in X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) experiments. From these complementary techniques, changes to structure, chemical environments, and electronic structure are observed as a function of X-ray exposure, allowing comparisons of stability to be made between the two catalysts. Radiation dose is estimated using recent developments to the RADDOSE-3D software for small molecules and applied to powder XRD and XPS experiments. Further insights into the electronic structure of the catalysts and changes occurring as a result of the irradiation are drawn from density functional theory (DFT). The techniques combined here offer much needed insight into the X-ray-induced effects in transition-metal catalysts and, consequently, their intrinsic stabilities. There is enormous potential to extend the application of these methods to other small molecular systems of scientific or industrial relevance.

Half-Heusler (HH) alloys are an important class of thermoelectric materials that combine promising performance with good engineering properties. This manuscript reports a variable temperature synchrotron x-ray diffraction study of several TiNiSn- and VFeSb-based HH alloys. A Debye model was found to capture the main trends in thermal expansion and atomic displacement parameters. The linear thermal expansion coefficient α(T) of the TiNiSn-based samples was found to be independent of alloying or presence of Cu interstitials with α av = 10.1 × 10−6 K−1 between 400 and 848 K. The α(T) of VFeSb and TiNiSn are well-matched, but NbFeSb has a reduced α av = 8.9 × 10−6 K−1, caused by a stiffer lattice structure. This is confirmed by analysis of the Debye temperatures, which indicate significantly larger bond force constants for all atomic sites in NbFeSb. This work also reveals substantial amounts of Fe interstitials in VFeSb, whilst these are absent for NbFeSb. The Fe interstitials are linked to low thermal conductivities, but also reduce the bandgap and lower the onset of thermal bipolar transport.

The authors thank the EPSRC for funding (Cation-Controlled Gating for Selective Gas Adsorption over Adaptable Zeolites: EP/N032942/1, V.M.G., P.A.W. and an NPIF Ph.D. scholarship for E.L.B.: EP/R512199/1). We acknowledge Diamond Light Source for time on Beamline I11 under Proposal CY22322-1. Experiments at the ISIS Neutron and Muon Source were supported by a beamtime allocation RB2090052-1 from the Science and Technology Facilities Council. The raw data accompanying this publication are directly available at https://doi.org/10.17630/cac904b4-3c07-4159-913f80ff53b13bb7 [reference 59] and, for the neutron powder diffraction data, https://doi.org/10.5286/ISIS.E.RB2090052-1 The lithium-exchanged form of a merlinoite zeolite (MER) with Si/Al = 4.2 (unit cell composition Li6.2Al6.2Si25.8O64) possesses a strongly contracted framework when dehydrated (the unit cell volume decreases by 12.9% from the hydrated ‘wide-pore’ form to the dehydrated ‘narrow-pore’ form). It shows cooperative adsorption behaviour for CO2, leading to two-step isotherms with the second step at elevated pressure (>2.5 bar at 298 K). Partially exchanging Na and K cations to give single phase Li,Na- and Li,K-MER materials reduces the pressure of this second adsorption step because the transition from narrow- to wide-pore forms upon CO2 adsorption occurs at lower partial pressures compared to that in Li-MER: partial exchange with Cs does not reduce the pressure of this transition. Exsolution effects are also seen at K cation contents >2.2 per unit cell. The phase transitions proceed via intermediate structures, by complex phase behaviour rarely seen for zeolitic materials. The strongly distorted narrow-pore structures adopted upon dehydration give one dimensional channel structures in which the percolation of CO2 through the material requires cation migration from their locations in ste sites. This is slow in Li3.4Cs2.8-MER where Cs cations occupy these critical ste cavities in the channels, causing very slow adsorption kinetics. As the partial pressure of CO2 increases, a threshold pressure is reached where cooperative adsorption and Cs cation migration occur and the wide-pore form results, with a three dimensionally connected pore system, leading to a sharp increase in uptake. This is far in excess of the increase of unit cell volume because more of the pore space becomes accessible. Strong hysteretic effects occur upon desorption, leading to CO2 encapsulation. CO2 remaining within the material after repeated adsorption/desorption cycles without heated activation improves sorption kinetics and modifies the stepped isotherms. Postprint Postprint

Tracing the transition between the diffuse atomic interstellar medium (ISM) and cold, dense gas is crucial for deciphering the star formation cycle in galaxies. Here we present MACH, a new survey of cold neutral hydrogen (HI) absorption at $21\rm\,cm$ by the Karl G. Jansky Very Large Array. We target 42 bright background sources with $600.001$ are ubiquitous ($c\sim100\%$), whereas high optical depths ($\tau>1$) are extremely rare ($c\sim0\%$)., Comment: 33 pages, 16 figures. Accepted for publication in ApJS

Bond formation and breakage is crucial upon energy storage in lithium transition metal oxides (LiMeO2, Me = Ni, Co, Mn), i.e., the conventional cathode materials in Li ion batteries. Near-edge X-ray absorption finestructure spectroscopy (NEXAFS) of the Me L and O K edge performed upon the first discharge of LiNixCo(1−x)/2Mn(1−x)/2O2 (x = 0.33: NCM111, x = 0.6: NCM622, x = 0.8: NCM811) in combination with charge transfer multiplet (CTM) calculations provide unambiguous evidence that redox reactions in NCMs proceed via a reversible oxidation of Ni associated with the formation of covalent bonds to O neighbors, and not, as widely assumed, via pure cationic or more recently discussed, pure anionic redox processes. Correlating these electronic changes with crystallographic data using operando synchrotron X-ray powder diffraction (SXPD) shows that the amount of ionic Ni limits the reversible capacity— at states of charge where all ionic Ni is oxidized (above 155 mAh g−1), the lattice parameters collapse, and irreversible reactions are observed. Yet the covalence of the Ni–O bonds also triggers the electronic structure and thus the operation potential of the cathodes.

Resolving the phase structure of neutral hydrogen (HI) is crucial for understanding the life cycle of the interstellar medium (ISM). However, accurate measurements of HI temperature and density are limited by the availability of background continuum sources for measuring HI absorption. Here we test the use of deep learning for extracting HI properties over large areas without optical depth information. We train a 1D convolutional neural network using synthetic observations of 3D numerical simulations of the ISM to predict the fraction of cold neutral medium (f_CNM) and the correction to the optically-thin HI column density for optical depth (R_HI) from $21\rm\,cm$ emission alone. We restrict our analysis to high Galactic latitudes ($|b|>30 deg), where the complexity of spectral line profiles is minimized. We verify that the network accurately predicts f_CNM and R_HI by comparing the results with direct constraints from 21 cm absorption. By applying the network to the GALFA-HI survey, we generate large-area maps of f_CNM and R_HI. Although the overall contribution to the total HI column of cold neutral medium (CNM)-rich structures is small (~5%), we find that these structures are ubiquitous. Our results are consistent with the picture that small-scale structures observed in 21 cm emission aligned with the magnetic field are dominated by CNM. Finally, we demonstrate that the observed correlation between HI column density and dust reddening (E(B-V)) declines with increasing R_HI, indicating that future efforts to quantify foreground Galactic E(B-V) using HI, even at high latitudes, should increase fidelity by accounting for HI phase structure., ApJ accepted

We have studied the small scale distribution of atomic hydrogen (HI) using 21-cm absorption spectra against multiple-component background radio continuum sources from the 21-SPONGE survey and the Millennium Arecibo Absorption Line Survey. We have found $>5\sigma$ optical depth variations at a level of $\sim0.03-0.5$ between 13 out of 14 adjacent sightlines separated by a few arcseconds to a few arcminutes, suggesting the presence of neutral structures on spatial scales from a few to thousands of AU (which we refer to as tiny scale atomic structure, TSAS). The optical depth variations are strongest in directions where the HI column density and the fraction of HI in the cold neutral medium (CNM) are highest, which tend to be at low Galactic latitudes. By measuring changes in the properties of Gaussian components fitted to the absorption spectra, we find that changes in both the peak optical depth and the linewidth of TSAS absorption features contribute to the observed optical depth variations, while changes in the central velocity do not appear to strongly impact the observed variations. Both thermal and turbulent motions contribute appreciably to the linewidths, but the turbulence does not appear strong enough to confine overpressured TSAS. In a majority of cases, the TSAS column densities are sufficiently high that these structures can radiatively cool fast enough to maintain thermal equilibrium with their surroundings, even if they are overpressured. We also find that a majority of TSAS is associated with the CNM. For TSAS in the direction of the Taurus molecular cloud and the local Leo cold cloud, we estimate densities over an order of magnitude higher than typical CNM densities., Comment: 29 pages, 19 figures, 4 tables. Accepted to ApJ. Section 4.3.1 updated from previous version

By tuning the tolerance factor, \(t\), of the Ruddlesden–Popper oxide Ca\(_2\)MnO\(_4\) through isovalent substitutions, we show that the uniaxial coefficient of linear thermal expansion (CLTE) of these systems can be systematically changed through large negative to positive values. Highresolution X-ray diffraction measurements show that the magnitude of uniaxial negative thermal expansion (NTE) increases as \(t\) decreases across the stability window of the NTE phase. Transitions to phases with positive thermal expansion (PTE) are found to occur at both the high-\(t\) and low-\(t\) limits of stability. First-principles calculations demonstrate that reducing \(t\) enhances the contribution to thermal expansion from the lowest frequency phonons, which have the character of octahedral tilts and have negative mode Gruneisen parameter components along the NTE axis. By tuning \(t\) to the lower edge of the NTE phase stability window, we are hence able to maximise the amplitudes of these vibrations and thereby maximise NTE with a CLTE of -8.1 ppm/K at 125 K. We also illustrate, at the other end of the phase diagram, that an enhancement in compliance of these materials associated with the rotational instability provides another mechanism by which NTE could be yet further enhanced in this and related systems.

We report on the structural, magnetic, and electronic properties of two new double-perovskites synthesized under high pressure; Pb2CaOsO6 and Pb2ZnOsO6. Upon cooling below 80 K, Pb2CaOsO6 simultaneously undergoes a metal--insulator transition and develops antiferromagnetic order. Pb2ZnOsO6, on the other hand, remains a paramagnetic metal down to 2 K. The key difference between the two compounds lies in their crystal structure. The Os atoms in Pb2ZnOsO6 are arranged on an approximately face-centred cubic lattice with strong antiferromagnetic nearest-neighbor exchange couplings. The geometrical frustration inherent to this lattice prevents magnetic order from forming down to the lowest temperatures. In contrast, the unit cell of Pb2CaOsO6 is heavily distorted up to at least 500 K, including antiferroelectric-like displacements of the Pb and O atoms despite metallic conductivity above 80 K. This distortion relieves the magnetic frustration, facilitating magnetic order which in turn drives the metal--insulator transition. Our results suggest that the phase transition in Pb2CaOsO6 is spin-driven, and could be a rare example of a Slater transition., Comment: 14 pages, 9 figures. Accepted as a regular article in Phys. Rev. B

We compare observations of HI from the Very Large Array (VLA) and the Arecibo Observatory and observations of HCO$^+$ from the Atacama Large Millimeter/submillimeter Array (ALMA) and the Northern Extended Millimeter Array (NOEMA) in the diffuse ($A_V\lesssim1$) interstellar medium (ISM) to predictions from a photodissociation region (PDR) chemical model and multi-phase ISM simulations. Using a coarse grid of PDR models, we estimate the density, FUV radiation field, and cosmic ray ionization rate (CRIR) for each structure identified in HCO$^+$ and HI absorption. These structures fall into two categories. Structures with $T_s40~\mathrm{K}$, mostly with $N(\mathrm{HCO^+})\gtrsim10^{12}~\mathrm{cm^{-2}}$, are consistent with high density, FUV radiation field, and CRIR models, characteristic of environments close to massive star formation. The latter are also found in directions with a significant fraction of thermally unstable HI. In at least one case, we rule out the PDR model parameters, suggesting that alternative mechanisms (e.g., non-equilibrium processes like turbulent dissipation and/or shocks) are required to explain the observed HCO$^+$ in this direction. Similarly, while our observations and simulations of the turbulent, multi-phase ISM agree that HCO$^+$ formation occurs along sightlines with $N(\mathrm{HI})\gtrsim10^{21}~\mathrm{cm^{-2}}$, the simulated data fail to explain HCO$^+$ column densities $\gtrsim\rm{few}\times10^{12}~\mathrm{cm^{-2}}$. Since a majority of our sightlines with HCO$^+$ had such high column densities, this likely indicates that non-equilibrium chemistry is important for these lines of sight., 15 pages, 3 figures, 1 table. Accepted to ApJ

Liquid oceans and ice caps, along with ice crusts, have long been considered defining features of the Earth, but space missions and observations have shown that they are in fact common features among many of the solar system's outer planets and their satellites. Interactions with rock-forming materials have produced saline oceans not dissimilar in many respects to those on Earth, where mineral precipitation within frozen seawater plays a significant role in both determining global properties and regulating the environment in which a complex ecosystem of extremophiles exists. Since water is considered an essential ingredient for life, the presence of oceans and ice on other solar system bodies is of great astrobiological interest. However, the details surrounding mineral precipitation in freezing environments are still poorly constrained, owing to the difficulties of sampling and ex situ preservation for laboratory analysis, meaning that predictive models have limited empirical underpinnings. To address this, the design and performance characterization of a transmission-geometry sample cell for use in long-duration synchrotron X-ray powder diffraction studies of in situ mineral precipitation from aqueous ice–brine systems are presented. The cell is capable of very slow cooling rates (e.g. 0.3°C per day or less), and its performance is demonstrated with the results from a year-long study of the precipitation of the hydrated magnesium sulfate phase meridianiite (MgSO4·11H2O) from the MgSO4–H2O system. Evidence from the Mars Rover mission suggests that this hydrated phase is widespread on the present-day surface of Mars. However, as well as the predicted hexagonal ice and meridianiite phases, an additional hydrated sulfate phase and a disordered phase are observed.

peer-reviewed A nonporous square lattice (sql) coordination network [Co(bipy)2(NCS)2]n (sql-1-Co-NCS) exhibits recyclable switching induced by CO2. The sorption isotherms are stepped with moderate hysteresis, temperature controlled and saturation uptake is fixed. Such switching, which has rarely been observed, offers the promise of exceptional working capacity for gas storage.

Aromatic and heterocyclic molecules which form electronically complementary π–π stacked complexes have recently found extensive application in functional materials, molecular machines, and stimuli-responsive supramolecular polymers. Here we describe the design and synthesis of model compounds that self-assemble through complementary stacking motifs, paralleling those postulated to exist in high-molecular weight, healable, supramolecular polymer systems. Complexation studies using 1H NMR and UV–vis spectroscopy indicated formation of a complementary complex between a π-electron rich dipyrenyl tweezer-motif and a tweezer-like, π-electron deficient bis-diimide. The binding stoichiometry in solution between the chain-folding diimide and the pyrenyl derivative was equimolar with respect to the two binding motifs, and the resulting association constant was measured at Ka = 1200 ± 90 M–1. Single crystal X-ray analysis of this “tweezer–tweezer” complex showed a low-energy conformation of the triethylenedioxy link...

The solid state structures of the di-cationic (1a) and radical mono-cationic (1b) redox forms of a 4,4′-bipyridinium (viologen) containing macrocycle have been established by single crystal X-ray analysis. Formation of the radical cation has a dramatic effect on the molecular structure of the macrocycle. Addition of an electron to 1a both decreases the diameter of the ring cavity (from 8.5 to 7.8 Å) and drastically flattens the torsion angle between the two pyridinium residues in the viologen, reducing it from 48° to either 3° or 9° (two independent molecules). Moreover, a close association of these near-planar radical cation units drives the formation of a tetrameric supramolecular structure in the solid state.

Herein, we report the catalytic decarboxylation of γ-valerolactone (GVL) over Zn/ZSM-5 to butene, followed by aromatization at high yield with co-feeding of water. An evaluation of the catalytic performance after prolonged periods of time showed that a water molecule is essential to maintain the decarboxylation and aromatization activities and avoid rapid catalyst deactivation. Synchrotron X-ray powder diffraction and Rietveld refinement were then used to elucidate the structures of adsorbed GVL and immobilized Zn species in combination with EXAFS and NMR spectroscopy. A new route for the cooperative hydrolysis of GVL by framework Zn-OH and Brønsted acidic sites to butene and then to aromatic compounds has thus been demonstrated. The structures and fundamental pathways for the nucleophilic attack of terminal Zn-OH sites are comparable to those of Zn-containing enzymes in biological systems.

The world’s first dedicated synchrotron instrument for long-duration experiments has been built and commissioned at Diamond Light Source. The new beamline I11 user facility is designed for the study of slow kinetics in polycrystalline materials., A new synchrotron X-ray powder diffraction instrument has been built and commissioned for long-duration experiments on beamline I11 at Diamond Light Source. The concept is unique, with design features to house multiple experiments running in parallel, in particular with specific stages for sample environments to study slow kinetic systems or processes. The instrument benefits from a high-brightness X-ray beam and a large area detector. Diffraction data from the commissioning work have shown that the objectives and criteria are met. Supported by two case studies, the results from months of measurements have demonstrated the viability of this large-scale instrument, which is the world’s first dedicated facility for long-term studies (weeks to years) using synchrotron radiation.

(1 − x)Na0.5Bi0.5TiO3-xKNbO3 (NBT-xKN) ceramics, with x in the range 0.01–0.09, were prepared by solid state reaction and conventional sintering. A progressive transformation from a nano-polar to a long-range ordered ferroelectric phase was observed after the application of a cyclic electric field with an amplitude of 5 kV mm−1. It is shown by analysis of the crushed ceramic pellets, using high resolution synchrotron x-ray diffraction, that the application the cyclic electric field induced an irreversible transformation from a pseudo-cubic nano-polar phase to a rhombohedral ordered ferroelectric phase having R3c symmetry. Furthermore, a systematic variation, from 89.6° to 90°, was observed in the rhombohedral interaxial angle as the KN content increased from 1 to 9%. By comparing the structural evidence with the ferroelectric polarization-electric field hysteresis loops, it is shown that the electric field-induced transformation is partially reversible for NBT-5KN and completely reversible or nonexistent for NBT-9KN.

We report the precise postsynthetic control of the composition of β‐Fe1+xSe by electrochemistry with simultaneous tracking of the associated structural changes via in‐situ synchrotron X‐ray diffraction. We access the full phase width of 0.01 < x < 0.04 and identify the superconducting state below 8 K, which in contrast to earlier reports is independent of the composition. However, in a second set of in‐situ X‐ray diffraction experiments, we demonstrate that β‐Fe1+xSe forms a new phase in the presence of oxygen above a 100 °C which has the same anti‐PbO type structure but is not superconducting down to 1.8 K. The latter process can be reversed electrochemically to reinstate the superconducting state. These observations exploit the exquisite control afforded by electrochemistry in contrast with classical approaches of chemical synthesis.

We report the precise postsynthetic control of the composition of β-Fe