Partial Structure Factors Research Articles

Development of Neural Network Potentials for Studying Chemical Behaviors of La3+/Nd3+ Ions in Molten LiCl-KCl-CsCl in Combination with Raman Spectroscopy.

The chemistry of molten salts has attracted great research interest owing to their wide applications in diverse fields. In the pyrochemical reprocessing of spent nuclear fuel or molten salt nuclear reactors, lanthanide elements as the principal fission products bring about changes in the composition and properties of molten salts. Herein, we report a comprehensive study on the coordination chemistry of the representative trivalent lanthanide ions (La3+/Nd3+) in LiCl-KCl-CsCl using a multiscale strategy combining Raman spectroscopy, deep learning, and large-scale molecular dynamics (MD) simulations. The neural network potential (NNP)-based MD and Raman spectroscopy studies revealed that La3+/Nd3+ ions prefer to form persistent octahedron complexes with the six-coordinated species as the dominant species at high temperatures. Compared to LaCl63-, NdCl63- shows higher stability with obviously longer lifetimes in LiCl-KCl-CsCl, as confirmed by the observed stronger interaction of Nd3+-Cl- pairs. The total and partial structure factors further indicated the formation of a more stable network structure in LiCl-KCl-CsCl containing NdCl3. Besides, the temperature exerts a larger influence on the local structures of the La3+ species compared to the Nd3+ analogues. According to the potential mean force calculations, the bond dissociation energies follow the order Ln-Cl > Li-Cl > K-Cl > Cs-Cl in LiCl-KCl-CsCl-LnCl3. The NNP-based large-scale MD simulations have been verified to be an efficient and powerful way in molten salt chemistry research.

Measurable structure factors of dense dispersions containing polydisperse optically inhomogeneous particles.

Here, it is investigated how optical properties of single scatterers in interacting multi-particle systems influence measurable structure factors. Both particles with linear gradients of their scattering length density and core-shell structures evoke characteristic deviations between the weighted sum 〈S(Q)〉 of partial structure factors in a multi-component system and experimentally accessible measurable structure factors S M(Q). While 〈S(Q)〉 contains only the structural information of self-organizing systems, S M(Q) is additionally influenced by the optical properties of their constituents, resulting in features such as changing amplitudes, additional peaks in the low-wavevector region or splitting of higher-order maxima, which are not related to structural reasons. It is shown that these effects can be systematically categorized according to the qualitative behaviour of the form factor in the Guinier region, which enables assessing the suitability of experimentally obtained structure factors to genuinely represent the microstructure of complex systems free from any particular model assumption. Hence, a careful data analysis regarding size distribution and optical properties of single scatterers is mandatory to avoid a misinterpretation of measurable structure factors.

Unveiling the thermodynamic landscape of liquid Ti–Al–Ni alloys through first-principles simulations

We conducted ab initio molecular dynamics simulations to systematically examine the composition-dependent thermodynamic properties and atomic-scale interactions in liquid Ti–Al–Ni alloys throughout the entire ternary phase space at 2033 K. The calculated enthalpies of mixing demonstrated exothermic tendencies, with a distinct minimum in the composition of Ti0.0Al0.50Ni0.50, indicating significant Al–Ni attractive interactions. Incorporating ternary interaction parameters into the Redlich-Kister-Muggianu equation enabled accurate modeling of the complex variations in mixing enthalpy. Analysis of partial pair correlation functions and structure factors revealed chemical and topological short-range ordering (SRO), as well as medium-range ordering, within the liquid alloy. Quantifying deviations from ideal configurational entropy clarifies the coupling between chemical SRO and topological SRO, significantly impacting the overall Gibbs energy of mixing. This comprehensive atomistic study provides insights into the thermodynamics of Ti–Al–Ni alloys, paving the way for tailoring their properties for high-performance applications.

Rescaled mode-coupling scheme for the quantitative description of experimentally observed colloid dynamics.

We describe experimentally observed collective dynamics in colloidal suspensions of model hard-sphere particles using a modified mode coupling theory (MCT). This rescaled MCT is capable of describing quantitatively the wave-vector and time-dependent diffusion in these systems. Intermediate scattering functions of liquidlike structured dispersions are determined by means of static and dynamic light-scattering experiments. The structure and short-time dynamics of the systems can be described quantitatively employing a multicomponent Percus-Yevick ansatz for the partial structure factors and an effective, one-component description of hydrodynamic interactions based on the semianalytical δγ expansion. Combined with a recently proposed empirical modification of MCT in which memory functions are calculated using effective structure factors at rescaled number densities, the scheme is able to model the collective dynamics over the entire accessible time and wave-vector range and predicts the volume-fraction-dependence of long-time self-diffusion coefficients and the zero-shear viscosity quantitatively. This highlights the potential of MCT as a practical tool for the quantitative analysis and prediction of experimental observations.

Alkali hydroxide (LiOH, NaOH, KOH) in water: Structural and vibrational properties, including neutron scattering results.

Structural and vibrational properties of aqueous solutions of alkali hydroxides (LiOH, NaOH, and KOH) are computed using quantum molecular dynamics simulations for solute concentrations ranging between 1 and 10M. Element-resolved partial radial distribution functions, neutron and x-ray structure factors, and angular distribution functions are computed for the three hydroxide solutions as a function of concentration. The vibrational spectra and frequency-dependent conductivity are computed from the Fourier transforms of velocity autocorrelation and current autocorrelation functions. Our results for the structure are validated with the available neutron data for 17M concentration of NaOH in water [Semrouni et al., Phys. Chem. Chem. Phys. 21, 6828 (2019)]. We found that the larger ionic radius [rLi+<rNa+<rK+] and higher concentration disturb the hydrogen-bond network of water, resulting in more disordered cationic hydration shell. Our abinitio simulation data for solute concentrations ranging between 1 and 10M can be used to guide future elastic and inelastic neutron-scattering experiments.

Local structure of concentrated NaFSA solutions in propylene carbonate studied by X-ray and neutron diffraction methods

Abstract The microscopic structure of 10 mol% NaFSA [FSA: bis(fluorosulfonyl)amide]-propylene carbonate (PC) solution has been investigated by means of X-ray and neutron diffraction techniques. The solvation structure of Na+ has been determined from least-squares fitting analysis of X-ray intermolecular difference interference terms observed for 10 mol% NaFSA-PC solution and pure liquid PC. In the present solution, onaverage, 6(1) PC molecules are involved in the first solvation shell of Na+ with intermolecular distance rNaO = 2.26(7) Å, and bond angle ∠Na+…O = C = 169(9)°. Intermolecular correlation between neighboring PC molecules in the solution has been derived from simultaneous least-squares fitting analysis of observed H–H, H–X, and X–X (X: atoms except for H) intermolecular partial structure factors determined from neutron diffraction data for H/D isotopically-substituted sample solutions. An indication of anti-parallel configuration of the nearest neighbor PC molecules has been suggested.

Decomposition of liquid-liquid extraction organic phase structure into critical and pre-peak contributions

Solution nanostructure induced by amphiphile self-association plays an important role in various chemical and physical processes, including liquid-liquid extraction (LLE). Small angle scattering techniques are an essential means of probing this structure, but, due to non-uniqueness of scattering patterns, their interpretation is not trivial. Here, we decompose small angle x-ray scattering (SAXS) patterns for a range of binary LLE organic phases into two components: Ornstein-Zernike and pre-peak contributions resulting from, respectively, critical concentration fluctuations and packing of the amphiphilic extractant molecules in the nonpolar aliphatic diluent. While we previously applied Ornstein-Zernike scattering models to similar organic phases, including the pre-peak explicitly in the fit allows us to measure weak fluctuations at high extractant concentration and simultaneously obtain information on the position and intensity of the correlation peak related to amphiphile packing. Scattering patterns and partial structure factors calculated from molecular dynamics simulations support this interpretation. We demonstrate how this minimal scattering model describes nanostructuring for a large number of extractant types over their entire extractant/diluent composition ranges, suggesting simple and universal behavior. The straightforward assignment of these structural contributions facilitates the comparison of these features between different classes of extractant molecules and will enable further studies of organic phase aggregation. Applicability to more complex, process-relevant organic phases is illustrated with post-contact organic phases containing significant quantities of extracted lanthanide nitrate salt, which we find are readily described by this model.

Effect of preparation conditions on the structure of As-Se glasses: Reverse Monte Carlo simulation

As an extension to part I, Dongol and Elhady (2020), the method of Reverse Monte Carlo simulation has been used to examine the effect of quenching rate on the structure of glassy AsxSe100−x (x=20, 30, 40, 50 at%). Results of the partial structure factors indicate that the correlations responsible for medium range order depend strongly on As-content, and distortion occurs in this structure range with increasing quenching rate. This distortion is more predominant in case of As50Se50 glass. Results of partial pair distribution function show that, most of short range order is mainly governed by the chemically ordered network model, and the random covalent network model plays a relatively small role. Also, it was clarified that the percentage of homopolar bonds increases with increasing quenching rate. In case of x=50at.%, the tendency of As segregation and formation of As–As bonds is demonstrated. Some Deviation from “8-N” rule was observed in the structure of the investigated glasses.

Ab initio study of collective eigenmodes in dynamics of molten salts

An effective fitting scheme within the thermo-viscoelastic model is proposed for estimation of dynamic eigenmodes of an ionic melt from ab initio molecular dynamics (AIMD) simulations. Dynamic eigenmodes are solutions of the generalized Langevin equation in matrix form, obtained on the basis set of eight dynamic variables. Fitting parameters are used only in the generalized hydrodynamic matrix T(k) for matrix elements involving heat density and heat current correlations only, because of huge computational efforts needed to calculate them directly in ab initio simulations. In the proposed scheme six AIMD-derived time correlation functions, three partial density-density and three partial current-current ones, are recovered by the proposed theoretical approach, which satisfies the exact sum rules up to the fourth frequency moments of partial dynamic structure factors. The suggested theoretical analysis was applied to estimation of propagating hydrodynamic and non-hydrodynamic eigenmodes in molten NaCl.

On the absence of structure factors in concentrated colloidal suspensions and nanocomposites.

Small-angle scattering is a commonly used tool to analyze the dispersion of nanoparticles in all kinds of matrices. Besides some obvious cases, the associated structure factor is often complex and cannot be reduced to a simple interparticle interaction, like excluded volume only. In recent experiments, we have encountered a surprising absence of structure factors (S(q) = 1) in scattering from rather concentrated polymer nanocomposites (Genix et al. in ACS Appl Mater Interfaces 11(19):17863-17872, 2019). In this case, quite pure form factor scattering is observed. This somewhat "ideal" structure is further investigated here making use of reverse Monte Carlo simulations in order to shed light on the corresponding nanoparticle structure in space. By fixing the target "experimental" apparent structure factor to one over a given q-range in these simulations, we show that it is possible to find dispersions with this property. The influence of nanoparticle volume fraction and polydispersity has been investigated, and it was found that for high concentrations only a high polydispersity allows reaching a state of S = 1. The underlying structure in real space is discussed in terms of the pair-correlation function, which evidences the importance of attractive interactions between polydisperse nanoparticles. The calculation of partial structure factors shows that there is no specific ordering of large or small particles, but that the presence of attractive interactions together with polydispersity allows reaching an almost "structureless" state.

Chemically ordered structure and dynamics in Al80Ti20 liquids

We conducted ab initio molecular dynamics simulations to study the structural and dynamical properties in Al80Ti20 liquids. The prepeak that represents some chemically ordered structure, emerges in the partial static structure factors at low temperatures. By calculating coordination numbers, we found a preferred connection for Al–Ti pairs, which induces an excess Ti/Al concentration around the central Al/Ti atoms. An excess Ti concentration is even found in the second neighbour shells around Ti atoms, rationalizing the prepeak as the result of chemical concentration fluctuation in these neighbour shells. Concomitantly, slow structural relaxation occurs below 1400K, exhibited as the second step relaxation in self-intermediate scattering function. The slow dynamics induces a non-Arrhenius transition for the temperature-dependent diffusivity and structural relaxation time, as well as the breakdown of the Stokes–Einstein relation. These results unveil the detailed ordering structure for the chemical interaction and the associated dynamical behaviour in Al80Ti20 liquids.

Study of beyond nearest-neighbor environment and intermediate-range order in a sodium aluminosilicate geopolymer using Reverse Monte Carlo modeling

A large scale three-dimensional structural model of a geopolymer with an approximate composition of NaAlSi2O6.5.5H2O obtained by Reverse Monte Carlo (RMC) modeling based on experimental high-energy x-ray diffraction is presented for the first time in order to obtain information regarding beyond nearest-neighbor environment and intermediate-range order (IRO). RMC model exhibits a three-dimensional network consisting of randomly cross-linked AlO4 and SiO4 tetrahedral units with uniformly distributed Na atoms and H2O molecules. The bond angle distributions, i.e. T-O-T, O-T-O and Na-O-Na angles, are somewhat distorted with lower values compared to analogous crystal systems. The origin of the first peak in the structure factor indicating IRO is investigated using the partial structure factors; Na-Na, Si-Na, Al-Si, O-H, and H-H atom pairs are found to be the main contributors. Ring size distribution analysis demonstrates that the structure mainly involves 6-, 7- and 8-membered rings. The coherence length of these IRO characteristics is ∼10.3 Å.

Impact of Dispersion Force Schemes on Liquid Systems: Comparing Efficiency and Drawbacks for Well-Targeted Test Cases.

First-principles molecular dynamics (FPMD) calculations were performed on liquid GeSe4 with the aim of inferring the impact of dispersion (van der Waals, vdW) forces on the structural properties. Different expressions for the dispersion forces were employed, allowing us to draw conclusions on their performances in a comparative fashion. These results supersede previous FPMD calculations obtained in smaller systems and shorter time trajectories by providing data of unprecedented accuracy. We obtained a substantial agreement with experiments for the structure factor regardless of the vdW scheme employed. This objective was achieved by using (in addition to FPMD with no dispersion forces) a selection of vdW schemes available within density functional theory. The first two are due to Grimme, D2 and D3, and the third one is devised within the so-called maximally localized Wannier functions approach (MLWF). D3 results feature a sizeable disagreement in real space with D2 and MLWF in terms of the partial and total pair correlation functions as well as the coordination numbers. More strikingly, total and partial structure factors calculated with D3 exhibit an unexpected sharp increase at low k. This peculiarity goes along with large void regions within the network, standing for a phase separation of indecipherable physical meaning. In view of these findings, further evidence of unconventional structural properties found by employing D3 is presented by relying on results obtained for a complex ionic liquid supported on a solid surface. The novelty of our study is multifold: new, reliable FPMD data for a prototypical disordered network system, convincing agreement with experimental data and assessment of the impact of dispersion forces, with emphasis on the intriguing behavior of one specific recipe and the discovery of common structural features shared by drastically dissimilar physical systems when the D3 vdW scheme is employed.

Experimental Determination of Deviation from Spherical Electron Densities of Atoms in Benzene Molecules in the Liquid State

Abstract Deviation of electron distribution around atomic nuclei from the spherical density in liquid benzene has directly been obtained through a X-ray–neutron difference interference function derived from the difference between the intermolecular X-ray diffraction interference term and the linear combination of neutron intermolecular partial structure factors weighted by atomic scattering factors for the X-ray scattering. The difference distribution function exhibits a broad negative peak at around r = 3.24 Å corresponding to intermolecular distance in which electron density is relatively lower than that for the spherical case. Positive peaks found at r = 4.30, 5.22, and 6.20 Å indicate intermolecular distances with higher electron density. This experimental evidence for intermolecular electron distribution in the liquid benzene has been discussed by means of the average molecular geometry of the nearest neighbor benzene molecules which was determined from the least squares analyses of observed neutron intermolecular partial structure factors.

Structure of molten NaCl and the decay of the pair-correlations.

The structure of molten NaCl is investigated by combining neutron and x-ray diffraction with molecular dynamics simulations that employed interaction potentials with either rigid or polarizable ions. Special attention is paid to the asymptotic decay of the pair-correlation functions, which is related to the small-k behavior of the partial structure factors, where k denotes the magnitude of the scattering vector. The rigid-ion approach gives access to an effective restricted primitive model in which the anion and cation have equal but opposite charges and are otherwise identical. For this model, the decay of the pair-correlation functions is in qualitative agreement with simple theory. The polarizable ion approach gives a good account of the diffraction results and yields thermodynamic parameters (density, isothermal compressibility, Debye screening length, and heat capacity) in accord with experiment. The longest decay length for the partial pair-distribution functions is a factor of ≃2.5 times greater than the nearest-neighbor distance. The results are commensurate with the decay lengths found for the effective restricted primitive model, which are much shorter than those found in experiments on concentrated electrolytes or ionic liquids using surface force apparatus.

Formulation of the partial structure factors and of the order parameters for the liquid or amorphous multicomponent alloy – Application to the quinternary and hexa-component alloys

Thanks to the extension of the results of our four previous works (B. Grosdidier 2018, 2019, 2021, 2022), we now study the structure and the order parameters of the multicomponent alloy in two conceptualizations by working in a “physical basis”. In this basis, all the structural quantities and the order parameters are formulated by very concise equations, in which the number of components does not explicitly appear. These equations allow a fast calculation of the total structure factors and also the investigation of properties valid for any number of species for several “toy models” having specific behavior of their atomic species. Some of our results are confirmed by studying the atom exchanges in several iso-stoichiometric multicomponent alloys. From these equations, we provide a protocol of the calculation for all partial and total structure factors of the hexa-component alloy, which can be reduced to a quinternary, quaternary and finally ternary system.

X-ray diffraction study and molecular dynamic simulation of liquid Al-Cu alloys: a new data and interatomic potentials comparison.

The experimental X-ray diffraction study of the Al[Formula: see text]Cu[Formula: see text] (at 1010 and 1310[Formula: see text]C) and Al[Formula: see text]Cu[Formula: see text] (at 1100 and 1400[Formula: see text]C) melts was performed. MD simulation of the Al[Formula: see text]Cu[Formula: see text], Al[Formula: see text]Cu[Formula: see text], Al[Formula: see text]Cu[Formula: see text], Al[Formula: see text]Cu[Formula: see text], Al[Formula: see text]Cu[Formula: see text], and Al[Formula: see text]Cu[Formula: see text] melts was carried out using several interatomic interaction potentials. It was found that the best agreement with experimental structural and transport data was achieved using the bond-order potential for the Al-Cu melts with predominant content of aluminum and embedded atom method potential for the Cu-based binary melts. The detailed analyses of short-range order in the Al-Cu melts were performed using partial structure factor and pair correlation function calculated from MD models. The formation of the chemical short-range order and medium-range order in the investigated melts was discussed.

Recombinant Plasminogen Activator Modified Nanoparticles for Targeting Thrombolysis in Branch Retinal Vein Occlusion.

Branch Retinal Vein Occlusion (BRVO) is the second chronic branch retinal vascular disease that causes abnormal vision loss after acute branch retinal disease in type 2 diabetes. There is no scientific conclusion about its specific pathogenic mechanism at present. Most clinical scholars generally support the theory that the partial human anatomical structure and various systemic risk psychological factors cause insufficient oxygen supply and hemostasis in the local branch retinal arteries. The research results of this article aim to reconstruct a non-nanocell-targeted thrombolytic drug delivery system without modification of rtPA without polyethylene glycol-methyl polycaprolactone and to re-evaluate its thrombus targeting and dissolution. The effect and safety of thrombus provide a new strategy for realizing combined treatment of thrombus. It is a study on the targeting of rtPA-NP to thrombus and its thrombolytic properties. HPLC method was used to detect the binding of fibrin clot prepared in vitro with coumarin-6 labeled NP and rtPA-NP; immunofluorescence technique was used to observe the location of nanomedicine and fibrin clot in branch retinal vein occlusion model Condition. The rtPA-NP drug delivery system constructed in this study not only retains the activity of rtPA and good thrombus targeting but also significantly prolongs its half-life and simplifies the way of administration. The therapeutic efficiency of rtPA-NP thrombus targeted administration on branch retinal vein occlusion reached 85.64%. The successful construction of the rtPA-NP thrombus targeted drug delivery system provides a new way for thrombosis treatment and lays the foundation for the future combination of anticoagulants and vascular protection drugs to achieve the combined treatment of thrombosis and the development of safe and efficient thrombolytic drugs.

Computation of Structure and Electrical Resistivity of Liquid Na-Rb Alloys

The structure and electrical resistivity of Na1-xRbx binary alloys (where x = 0, 0.1, 0.2,…,1) are computed using Percus-Yevick (PY) equation, hard-sphere model and Faber-Ziman formula respectively. The partial structure factors and total structure factor are computed using hard-sphere model for Na1-xRbx. In the calculation of resistivity using Faber-Ziman formula, we have employed Ashcroft empty-core pseudo-potential and Hartree dielectric screening. Calculated values of resistivity are compared with the experimental results and other theoretical values reported in literature. It is found that the electrical resistivity calculated using Faber-Ziman formula for binary alloy Na1-xRbx is in good agreement with the values reported experimentally.

Structure-induced order – disorder transformation in Cd – Na liquid alloys

Abstract The origins of the S-shaped entropy of mixing and order – disorder transformation in Cd –Na liquid alloys have been investigated within a first-principle approach of a pseudo-potential perturbation scheme with the Gibbs–Bogoliubov variation technique.We find that the deepening of the structure part of the entropy around the stoichiometric composition (c Na ≈ 0.33) is responsible for the S-shaped entropy and suggests the existence of short-range order in the liquid state. The role of the local-field correction function, G(q), of conduction electrons on the entropy of mixing is examined. The impact of G(q) on partial structure factors is more visible towards low q (q → 0) than at higher q.