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Silicate glasses containing silicon, sodium, phosphorous, and calcium have the ability to promote bone regeneration and biodegrade as new tissue is generated. Recently, it has been suggested that adding SrO can benefit tissue growth and silicate glass dissolution. Motivated by these recent developments, the effect of SrO/CaO-CaO/SrO substitution on the local structure and dynamics of Si-Na-P-Ca-O oxide glasses has been studied in this work. Differential thermal analysis has been performed to determine the thermal stability of the glasses after the addition of strontium. The local structure has been studied by neutron diffraction augmented by Reverse Monte Carlo simulation, and the local dynamics by neutron Compton scattering and Raman spectroscopy. Differential thermal analysis has shown that SrO-containing glasses have lower glass transition, melting, and crystallisation temperatures. Moreover, the addition of the Sr 2+ ions decreased the thermal stability of the glass structure. The total neutron diffraction augmented by the RMC simulation revealed that Sr played a similar role as Ca in the glass structure when substituted on a molar basis. The bond length and the coordination number distributions of the network modifiers and network formers did not change when SrO (x = 0.125, 0.25) was substituted for CaO (25-x). However, the network connectivity increased in glass with 12.5 mol% CaO due to the increased length of the Si-O-Si interconnected chain. The analysis of Raman spectra revealed that substituting CaO with SrO in the glass structure dramatically enhances the intensity of the high-frequency band of 1110-2000 cm -1 . For all glasses under investigation, the changes in the relative intensities of Raman bands and the distributions of the bond lengths and coordination numbers upon the SrO substitution were correlated with the values of the widths of nuclear momentum distributions of Si, Na, P, Ca, O, and Sr. The widths of nuclear momentum distributions were observed to soften compared to the values observed and simulated in their parent metal-oxide crystals. The widths of nuclear momentum distributions, obtained from fitting the experimental data to neutron Compton spectra, were related to the amount of disorder of effective force constants acting on individual atomic species in the glasses.

The growing scale of the devastation that even a single terrorist attack can cause requires more effective methods for the detection of hazardous materials. In particular, there are no solutions for effectively monitoring threats at sea, both for the off-shore infrastructure and ports. Currently, state-of-the-art detection methods determine the density distribution and the shapes of tested subjects but only allow for a limited degree of substance identification. This work aims to present a feasibility study of the possible usage of several methods available on the thermal-to-epithermal neutron station, VESUVIO, at the ISIS neutron and muon spallation source, UK, for the detection of hazardous materials. To this end, we present the results of a series of experiments performed concurrently employing neutron transmission and Compton scattering using melamine, a commonly used explosive surrogate, in order to determine its signal characteristics and limits of detection and quantitation. The experiments are supported by first-principles modelling, providing detailed scrutiny of the material structure and the nuclear dynamics behind the neutron scattering observables., (© 2024. Crown.)

This study presents a comprehensive analysis of the vibrational spectra of methyl-β-D-ribofuranoside. Employing a combination of inelastic neutron scattering, Raman, and infrared spectroscopy allows for the observation of all modes regardless of the selection rules. The experimental techniques were complemented by density functional theory computational methods using both gas-phase ( Gaussian ) and solid-state ( CRYSTAL , CASTEP ) approaches to provide an unambiguous assignment of the defining vibrational features. Two distinct structures of the molecule were identified in the unit cell, differentiated mainly by the orientation of the furanose ring O-H bonds. The low-energy region of the spectrum (<400 cm -1 ) is dominated by lattice vibrations and functional group rotation, while the midenergy region is dominated by out-of-plane bending motions of the furanose ring (400-900 cm -1 ) and by C-H bending in the methyl and methylene groups (1400-1600 cm -1 ). The high-energy region (>2800 cm -1 ) encompasses the C-H and O-H stretching modes and offers convincing evidence of at least one H-bonding interaction between the two structures of methyl-β-D-ribofuranoside.

Porous organic cages (POCs) are nanoporous materials composed of discrete molecular units that have uniformly distributed functional pores. The intrinsic porosity of these structures can be tuned accurately at the nanoscale by altering the size of the porous molecules, particularly to an optimal size of 3.6 Å, to harness the kinetic quantum sieving effect. Previous research on POCs for isotope separation has predominantly centered on differences in the quantities of adsorbed isotopes. However, nuclear quantum effects also contribute significantly to the dynamics of the sorption process, offering additional opportunities for separating H 2 and D 2 at practical operational temperatures. In this study, our investigations into H 2 and D 2 sorption on POC samples revealed a higher uptake of D 2 compared to that of H 2 under identical conditions. We employed quasi-elastic neutron scattering to study the diffusion processes of D 2 and H 2 in the POCs across various temperature and pressure ranges. Additionally, neutron Compton scattering was utilized to measure the values of the nuclear zero-point energy of individual isotopic species in D 2 and H 2. The results indicate that the diffusion coefficient of D 2 is approximately one-sixth that of H 2 in the POC due to the nuclear quantum effect. Furthermore, the results reveal that at 77 K, D 2 has longer residence times compared to H 2 when moving from pore to pore. Consequently, using the kinetic difference of H 2 and D 2 in a porous POC system enables hydrogen isotope separation using a temperature or pressure swing system at around liquid nitrogen temperatures.

Experimental protocols aiming at the characterisation of glass transition often suffer from ambiguity. The ambition of the present study is to describe the glass transition in a complex, micro heterogeneous system, the dry rice pasta, in a most unambiguous manner, minimising the influence of technique-specific bias. To this end, we apply an unprecedented combination of experimental techniques. Apart from the usually used NMR and DSC, we employ, in a concurrent manner, neutron transmission, diffraction, and Compton scattering. This enables us to investigate the glass transition over a range of spatio-temporal scales that stretches over seven orders of magnitude. The results obtained by neutron diffraction and DSC reveal that dry rice pasta is almost entirely amorphous. Moreover, the glass transition is evidenced by neutron transmission and diffraction data and manifested as a significant decrease of the average sample number density in the temperature range between 40 and 60 °C. At the microscopic level, our NMR, neutron transmission and Compton scattering results provide evidence of changes in the secondary structure of the starch within the dry rice pasta accompanying the glass transition, whereby the long-range order provided by the polymer structure within the starch present in the dry rice pasta is partially lost.

We present an experimental investigation of the hydrogen nuclear momentum distribution in biphenyl using deep inelastic neutron scattering. Our experimental results suggest that the local potential affecting hydrogen is both harmonic and isotropic within experimental uncertainties. This feature is interpreted as a consequence of the central limit theorem, whereby the three-dimensional momentum distribution is expected to become a purely Gaussian function as the number of independent vibrational modes in a system increases. We also performed ab initio phonon calculations on biphenyl and other saturated hydrocarbons, from methane to decane. From the results of the simulations, one can observe that the nuclear momentum distribution becomes more isotropic as the number of atoms and normal modes in the molecule increases. Moreover, the predicted theoretical anisotropy in biphenyl is clearly larger than in the experiment. The reason is that the total number of normal modes necessary to reproduce the experimental results is much larger than the number of normal modes encompassed by a single unit cell due to the presence of structural disorder and intermolecular interactions in the real crystal, as well as coupling of different normal modes. Finally, experimental data were collected, over a subset of detectors on the VESUVIO spectrometer at ISIS, with a novel setup to increase the count rate and signal-to-background ratio. We envision that such an optimized experimental setup can provide faster measurements and more stringent constraints for phonon calculations.

This work introduces the use of mass-selective neutron spectroscopy as an analytical tool for the quantitative and non-destructive detection of hydrogen in bulk media. To this end, systematic measurements have been performed on a series of polyethylene standards of known thickness and density, in order to establish optimal data-acquisition protocols as well as associated limits of detection and quantitation. From this analysis, we conclude that state-of-the-art epithermal-neutron instrumentation enables the detection of aeral molar densities of bulk hydrogen in the μmol cm -2 range. We also discuss potential improvements on the horizon, with a view to broadening the scope of the technique across chemistry, materials science, and engineering.

We apply a unique sequence of structural and dynamical neutron-scattering techniques, augmented with density-functional electronic-structure calculations, to establish the degree of polymorphism in an archetypal hydrogen-bonded system - crystalline formic acid. Using this combination of experimental and theoretical techniques, the hypothesis by Zelsmann on the coexistence of the β 1 and β 2 phases above 220 K is tested. Contrary to the postulated scenario of proton-transfer-driven phase coexistence, the emerging picture is one of a quantitatively different structural change over this temperature range, whereby the loosening of crystal packing promotes temperature-induced shearing of the hydrogen-bonded chains. The presented work, therefore, solves a fifty-year-old puzzle and provides a suitable framework for the use neutron-Compton-scattering techniques in the exploration of phase polymorphism in condensed matter.

High-resolution spectroscopic measurements using thermal and epithermal neutrons and first-principles calculations within the framework of density-functional theory are used to investigate the nuclear dynamics of light and heavy species in the metastable phase of caesium hydrogen sulfate. Within the generalised-gradient approximation, extensive calculations show that both 'standard' and 'hard' formulations of the Perdew-Burke-Ernzerhof functional supplemented by Tkatchenko-Scheffler dispersion corrections provide an excellent description of the known structure, underlying vibrational density of states, and nuclear momentum distributions measured at 10 and 300 K. Encouraged by the agreement between experiment and computational predictions, we provide a quantitative appraisal of the quantum contributions to nuclear motions in this solid acid. From this analysis, we find that only the heavier caesium atoms reach the classical limit at room temperature. Contrary to naïve expectation, sulfur exhibits a more pronounced quantum character relative to classical predictions than the lighter oxygen atom. We interpret this hitherto unexplored nuclear quantum effect as arising from the tighter binding environment of this species in this technologically relevant material.