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The bulk water density data are studied in a very large temperature–pressure range, from stable liquid to glass in the frame of water polymorphism. Because this thermodynamic variable evidences a crossover T*, above which the hydrogen bond (HB) is unable to arrange tetrahedral networks, the T-dependence of their isobars was considered. Such an analysis also shows pressure, P*, around which their thermal behaviors are completely different: concave below P* (with maxima and minima) and convex above (without extremes). Having ρ's measured values of the bimodal structures of the liquid phase, HDL (ρHDL), made of not-bonded monomers (ρNHB) and partially bonded dimers plus trimers (ρNHB), and LDL tetramers (ρLDL) the isobars of the relative distributions [W(P, T)] of the three species (WLDL, WPHB, and WNHB) have been evaluated. The results were studied by means of a logistic function (LF) that details the evolutions of the relative polpulations of the water LDL and HDL phases by decreasing T (for the isobars, in the range of 0.1–400 MPa). The LFs analysis obtained by proposing a full connection between liquid water from its supercooled metastable phase to the stable up to the boiling temperature identifies the Widom line quite satisfactorily and fully supports the presence of the liquid–liquid critical point in the deep supercooled region, located at about 190 K and in the range 200 > P > 180 MPa. [ABSTRACT FROM AUTHOR]

We present comprehensive numerical results from a study of model H, which describes phase separation kinetics in binary fluid mixtures. We study the pattern dynamics of both density and velocity fields in d = 2, 3. The density length scales show three distinct regimes, in accordance with analytical arguments. The velocity length scale shows a diffusive behavior. We also study the scaling behavior of the morphologies for density and velocity fields and observe dynamical scaling in the relevant correlation functions and structure factors. Finally, we study the effect of quenched random field disorder on spinodal decomposition in model H. [ABSTRACT FROM AUTHOR]

It is shown that the transport coefficients (self-diffusion, shear viscosity, and thermal conductivity) of the Weeks–Chandler–Andersen (WCA) fluid along isotherms exhibit a freezing density scaling (FDS). The functional form of this FDS is essentially the same or closely related to those in the Lennard-Jones fluid, hard-sphere fluid, and some liquefied noble gases. This proves that this FDS represents a quasi-universal corresponding state principle for simple classical fluids with steep interactions. Some related aspects, such as a Stokes–Einstein relation without a hydrodynamic diameter and gas-to-liquid dynamical crossover, are briefly discussed. Simple fitting formulas for the transport coefficients of the dense WCA fluid are suggested. [ABSTRACT FROM AUTHOR]

Experimental and theoretical advances for understanding the temperature of maximum density (TMD) of aqueous solutions are outlined. The main equations that relate the TMD behavior to key thermodynamic properties are stated. The experimental TMD data are classified as a function of the nature of the solute (inorganic electrolytes, non-electrolytes, organic salts and ionic liquids, and amino acids and proteins). In addition, the experimental results that explore the effect of pressure are detailed. These experimental data are rationalized by making use of qualitative and semi-quantitative arguments based on the thermodynamics of aqueous systems. The main theoretical and simulation advances in TMD for aqueous solutions are also shown—including new calculations in the context of the scaled particle theory—and their ability to reproduce the experimental data is evaluated. Finally, new experiments and theoretical and simulation developments, which could give important insights into the problem of TMD for aqueous solutions, are proposed. [ABSTRACT FROM AUTHOR]

In many modern applications, it is important to understand mechanisms of non-equilibrium chemistry and physics that are driven by low energy ion bombardment of solid surfaces. However, the study of these processes has been challenging as it demands a relatively unique balance between chemical fidelity and computational cost. To this end, we have proposed and constructed a new, high-throughput simulation pipeline based on density functional tight binding simulations. Additionally, we have extended the parameter set pbc-0-3 with the addition of Ar, thereby enabling the simulation of Ar bombardment. This pipeline was then applied to study the structural and compositional evolution of silicon nitride (SiN) under Ar bombardment. We identified a possible rate limiting step of bombardment-driven sputtering of SiN and suggested underlying mechanisms of Si and N removal. Damage from the bombardment, including generation of surface defects and Ar implantation, are further discussed. These findings and the newly developed simulation framework will serve as a useful foundation for further research in processes driven by ion bombardment. [ABSTRACT FROM AUTHOR]

In gas gun experiments, a graded density impactor (GDI) is used to achieve quasi-isentropic loading. However, inconsistency between the designed and experimental loading profiles, mainly caused by by-products during preparation, limits the application of GDI for a long time. In this work, a kind of W/Ti GDI with advantages of a wide density range of 4.5–19.3 g/cm3 and high structural designability was designed and synthesized. Each of mid-layers of the W/Ti GDI was composed of W and Ti without the formation of an intermetallic compound, and had good parallelism and flatness. This provides a prerequisite for good agreement between the designed and experimental loading profiles. Due to the high designability of the GDI, quasi-isentropic loading with different stress-paths was achieved by controlling the structure of the GDI. Then, independently controlling peak stress and strain rates of loading was successfully achieved by changing the flyer velocity and the type of the W/Ti GDI. The W/Ti GDI has enormous application potential in studying the dynamic response of materials under quasi-isentropic loading with stress and strain rate controlled. [ABSTRACT FROM AUTHOR]

The exchange-only virial relation due to Levy and Perdew is revisited. Invoking the adiabatic connection, we introduce the exchange energy in terms of the right-derivative of the universal density functional w.r.t. the coupling strength λ at λ = 0. This agrees with the Levy–Perdew definition of the exchange energy as a high-density limit of the full exchange–correlation energy. By relying on v-representability for a fixed density at varying coupling strength, we prove an exchange-only virial relation without an explicit local-exchange potential. Instead, the relation is in terms of a limit (λ ↘ 0) involving the exchange–correlation potential v x c λ , which exists by assumption of v-representability. On the other hand, a local-exchange potential vx is not warranted to exist as such a limit. [ABSTRACT FROM AUTHOR]

A synchrotron based vacuum ultraviolet absorption spectrum for γ-pyrone has been interpreted in terms of singlet excited electronic states using a variety of coupled cluster, configuration interaction, and density functional calculations. The extremely weak spectral onset at 3.557 eV shows eight vibrational peaks, which following previous analyses, are attributed to a forbidden 1A2 state. A contrasting broad peak with a maximum at 5.381 eV has a relatively high cross-section of 30 Mb; this arises from three overlapping states, where a 1A1 state dominates over progressively weaker 1B2 and 1B1 states. After fitting the second band to a polynomial Gaussian function and plotting the regular residuals over 20 vibrational peaks, we have had limited success in analyzing this fine structure. However, the small separation between these three states clearly shows that their vibrational satellites must overlap. Singlet valence and Rydberg state vibrational profiles were determined by configuration interaction using the CAM-B3LYP density functional. Vibrational analysis using both the Franck–Condon and Herzberg–Teller procedures showed that both procedures contributed to the profiles. Theoretical Rydberg states were evaluated by a highly focused CI procedure. The superposition of the lowest photoelectron spectral band on the vacuum ultraviolet spectrum near 6.4 eV shows that the 3s and 3p Rydberg states based on the 2B2 ionic state are present; those based on the other low-lying ionic state (X2B1) are destroyed by broadening; this is a dramatic extension of the broadening previously witnessed in our studies of halogenobenzenes. [ABSTRACT FROM AUTHOR]

Kohn–Sham density functional theory has been the most popular method in electronic structure calculations. To fulfill the increasing accuracy requirements, new approximate functionals are needed to address key issues in existing approximations. It is well known that nonlocal components are crucial. Current nonlocal functionals mostly require orbital dependence such as in Hartree–Fock exchange and many-body perturbation correlation energy, which, however, leads to higher computational costs. Deviating from this pathway, we describe functional nonlocality in a new approach. By partitioning the total density to atom-centered local densities, a many-body expansion is proposed. This many-body expansion can be truncated at one-body contributions, if a base functional is used and an energy correction is approximated. The contribution from each atom-centered local density is a single finite-range nonlocal functional that is universal for all atoms. We then use machine learning to develop this universal atom-centered functional. Parameters in this functional are determined by fitting to data that are produced by high-level theories. Extensive tests on several different test sets, which include reaction energies, reaction barrier heights, and non-covalent interaction energies, show that the new functional, with only the density as the basic variable, can produce results comparable to the best-performing double-hybrid functionals, (for example, for the thermochemistry test set selected from the GMTKN55 database, BLYP based machine learning functional gives a weighted total mean absolute deviations of 3.33 kcal/mol, while DSD-BLYP-D3(BJ) gives 3.28 kcal/mol) with a lower computational cost. This opens a new pathway to nonlocal functional development and applications. [ABSTRACT FROM AUTHOR]

The effect of changing magnetic parameters on the size and density of skyrmions in a hexagonal lattice is investigated using micromagnetic simulations. Achieving control of the skyrmion density, for instance, by applied voltages, is a route to magnetic neuromorphic computing devices. Here, we show how small changes in the uniaxial magnetic anisotropy and Dzyaloshinskii–Moriya interaction lead to large changes in the skyrmion size and density, which occurs for parameters that do not support isolated skyrmions. The effect of a grain structure on the density of skyrmions is modeled through the introduction of a locally varying anisotropy. This shows that a higher density of skyrmions is favored for a wider distribution of magnetic anisotropy. The results provide a clear understanding of systems where the skyrmion density can be externally controlled and assist the design of functional skyrmion-based devices. [ABSTRACT FROM AUTHOR]

Low-crosslinked polymer networks have recently been found to behave auxetically when subjected to small tensions, that is, their Poisson's ratio ν becomes negative. In addition, for specific state points, numerical simulations revealed that diamond-like networks reach the limit of mechanical stability, exhibiting values of ν = −1, a condition that we define as hyper-auxeticity. This behavior is interesting per se for its consequences in materials science but is also appealing for fundamental physics because the mechanical instability is accompanied by evidence of criticality. In this work, we deepen our understanding of this phenomenon by performing a large set of equilibrium and stress–strain simulations in combination with phenomenological elasticity theory. The two approaches are found to be in good agreement, confirming the above results. We also extend our investigations to disordered polymer networks and find that the hyper-auxetic behavior also holds in this case, still manifesting a similar critical-like behavior as in the diamond one. Finally, we highlight the role of the number density, which is found to be a relevant control parameter determining the elastic properties of the system. The validity of the results under disordered conditions paves the way for an experimental investigation of this phenomenon in real systems, such as hydrogels. [ABSTRACT FROM AUTHOR]

XYG3-type doubly hybrid (xDH) approximations have gained widespread recognition for their accuracy in describing a diverse range of chemical and physical interactions. However, a recent study [Song et al., J. Phys. Chem. Lett. 12, 800–807 (2021)] has highlighted the limitation of xDH methods in calculating the dissociation of NaCl molecules. This issue has been related to the density and orbitals used for evaluating the energy in xDH methods, which are obtained from lower-rung hybrid density functional approximations (DFAs) and display substantial density errors in the dissociation limit. In this work, we systematically investigate the influence of density on several challenging datasets and find that xDH methods are less sensitive to density errors compared to semi-local and hybrid DFAs. Furthermore, we demonstrate that the self-interaction corrected SCAN density approach offers superior accuracy compared to the self-consistent SCAN density and Hartree–Fock density approaches, as evidenced by performing charge analysis on the dissociation of heterodimers, such as NaCl and LiF. Building on these insights, we propose a five-parameter xDH method using the SCAN density and orbitals corrected by the PZ-SIC scheme. This new xDH@SCAN(SIC) method provides a balanced and accurate description across a wide range of challenging systems. [ABSTRACT FROM AUTHOR]

Separating the Coulomb potential into short-range and long-range components enables the use of different electron repulsion integral algorithms for each component. The short-range part can be efficiently computed using the analytical algorithm due to the locality in both the Gaussian-type orbital basis and the short-range Coulomb potentials. The integrals for the long-range Coulomb potential can be approximated with the density fitting method. A very small auxiliary basis is sufficient for the density fitting method to accurately approximate the long-range integrals. This feature significantly reduces the computational efforts associated with the N4 scaling in density fitting algorithms. For large molecules, the range separation and long-range density fitting method outperforms the conventional analytical integral evaluation scheme employed in Hartree–Fock calculations and provides more than twice the overall performance. In addition, this method offers a higher accuracy compared to conventional density fitting methods. The error in the Hartree–Fock energy can be easily reduced to 0.1 μEh per atom or smaller. [ABSTRACT FROM AUTHOR]

Density functional calculations of Rydberg excited states up to high energy are carried out for several molecules using an approach where the orbitals are variationally optimized by converging on saddle points on the electronic energy surface within a real space grid representation. Remarkably good agreement with experimental estimates of the excitation energy is obtained using the generalized gradient approximation (GGA) functional of Perdew, Burke, and Ernzerhof (PBE) when Perdew–Zunger self-interaction correction is applied in combination with complex-valued orbitals. Even without the correction, the PBE functional gives quite good results despite the fact that corresponding Rydberg virtual orbitals have positive energy in the ground state calculation. Results obtained using the Tao, Perdew, Staroverov, and Scuseria (TPSS) and r2SCAN meta-GGA functionals are also presented, but they do not provide a systematic improvement over the results from the uncorrected PBE functional. The grid representation combined with the projector augmented-wave approach gives a simpler and better representation of diffuse Rydberg orbitals than a linear combination of atomic orbitals with commonly used basis sets, the latter leading to an overestimation of the excitation energy due to confinement of the excited states. [ABSTRACT FROM AUTHOR]

Since the development of generalized gradient approximations in the 1990s, approximations based on density functional theory have dominated electronic structure theory calculations. Modern approximations can yield energy differences that are precise enough to be predictive in many instances, as validated by large- and small-scale benchmarking efforts. However, assessing the quality of densities has been the subject of far less attention, in part because reliable error measures are difficult to define. To this end, this work introduces the mean-field error, which directly assesses the quality of densities from approximations. The mean-field error is contextualized within existing frameworks of density functional error analysis and understanding and shown to be part of the density-driven error. It is demonstrated in several illustrative examples. Its potential use in future benchmarking protocols is discussed, and some conclusions are drawn. [ABSTRACT FROM AUTHOR]

Solving the Liouville–von-Neumann equation using a density operator provides a more complete picture of dynamical quantum phenomena than by using a wavepacket and solving the Schrödinger equation. As density operators are not restricted to the description of pure states, they can treat both thermalized and open systems. In practice, however, they are rarely used to study molecular systems as the computational resources required are even more prohibitive than those needed for wavepacket dynamics. In this paper, we demonstrate the potential utility of a scheme based on the powerful multi-layer multi-configurational time-dependent Hartree algorithm for propagating multi-dimensional density operators. Studies of two systems using this method are presented at a range of temperatures and including up to 13 degrees of freedom. The first case is single proton transfer in salicylaldimine, while the second is double proton transfer in porphycene. A comparison is also made with the approach of using stochastic wavepackets. [ABSTRACT FROM AUTHOR]

We present a novel diagnostic system, based on the principle of capacitive sensing, capable of detecting the conduction zone of detonating explosives. The method relies on measuring the change in the capacitive coupling between a printed circuit and its surroundings, induced by an increase in local conductivity. A high frequency wave generator provides the driving signal, which is modified by the change in coupling. This method boasts greater sensitivity than existing conductivity-based techniques, with comparable spatial and temporal resolution. The subject material was pentaerythritol tetranitrate (PETN) powder, pressed into low density (50%–85% theoretical maximum density) cylindrical columns. Previous attempts to measure the reaction zone of low density PETN have faced difficulties because of its short length and low conductivity compared to other explosives. The PETN was initiated using a laser flyer detonator in order to reach detonation promptly and with a minimum of electrical noise. Application of the capacitive sensor diagnostic and subsequent analysis yielded a density dependent steady-state reaction zone length of between 45 and 78 μ m. [ABSTRACT FROM AUTHOR]

Air refractive index alteration is an important research technique used to examine blast density and pressure. However, precise time-course measurements of refractive index changes at a fixed point caused by air blast waves are challenging due to the necessity for high precision and noise immunity. This study proposes a dual-probe, dual-frequency fiber-optic displacement interferometer that achieves nanometer-level accuracy and can tolerate light intensity fluctuations and transmission-fiber interference. The specially designed sensor enables the measurement of refractive index at a fixed point resulting from explosive-driven air blast waves, further allowing for obtaining the pressure and density information. [ABSTRACT FROM AUTHOR]

The use of oriented external electric fields (OEEFs) as a potential tool for catalyzing chemical reactions has gained traction in recent years. Electronic structure calculations using OEEFs are commonly done using methods based on density functional theory (DFT), but until now, the performance of DFT methods for calculating molecules in OEEFs had not been assessed in a more general scope. Looking at the accuracy of molecular geometries, electronic energies, and electric dipole moments compared to accurate coupled-cluster with perturbative triples data, we have investigated a wide variety of density functionals using different basis sets to determine how well the individual functionals perform on various types of chemical bonds. We found that most functionals accurately calculate geometries in OEEFs and that small basis sets are sufficient in many cases. Calculations of electronic energies show a significant error introduced by the OEEF, which the use of a larger basis set helps mitigate. Our findings show that DFT methods can be used for accurate calculations in OEEFs, allowing researchers to make full use of the advantages that they bring. [ABSTRACT FROM AUTHOR]

Comb-like polymers have shown potential as advanced materials for a diverse palette of applications due to the tunability of their polymer architecture. To date, however, it still remains a challenge to understand how the conformational properties of these polymers arise from the interplay of their architectural parameters. In this work, extensive simulations were performed using dissipative particle dynamics to investigate the effect of grafting density, backbone length, and sidechain length on the conformations of comb-like polymers immersed in a good solvent. To quantify the effect of these architectural parameters on polymer conformations, we computed the asphericity, radius of gyration, and backbone and sidechain end-to-end distances. Bond–bond correlation functions and effective Kuhn lengths were computed to quantify the topological stiffness induced by sidechain–sidechain interactions. Simulation results reveal that the effective Kuhn length increases as grafting density and sidechain length increase, in agreement with previous experimental and theoretical studies. This increase in stiffness results in comb-like polymers adopting extended conformations as grafting density and sidechain length increase. Simulation results regarding the radius of gyration of comb-like polymers as a function of grafting density are compared with scaling theory predictions based on a free energy proposed by Morozova and Lodge [ACS Macro Lett. 6, 1274–1279 (2017)] and scaling arguments by Tang et al. [Macromolecules 55, 8668–8675 (2022)]. [ABSTRACT FROM AUTHOR]

Density functional theory is the workhorse of chemistry and materials science, and novel density functional approximations are published every year. To become available in program packages, the novel density functional approximations (DFAs) need to be (re)implemented. However, according to our experience as developers of Libxc [Lehtola et al., SoftwareX 7, 1 (2018)], a constant problem in this task is verification due to the lack of reliable reference data. As we discuss in this work, this lack has led to several non-equivalent implementations of functionals such as Becke–Perdew 1986, Perdew–Wang 1991, Perdew–Burke–Ernzerhof, and Becke's three-parameter hybrid functional with Lee–Yang–Parr correlation across various program packages, yielding different total energies. Through careful verification, we have also found many issues with incorrect functional forms in recent DFAs. The goal of this work is to ensure the reproducibility of DFAs. DFAs must be verifiable in order to prevent the reappearance of the above-mentioned errors and incompatibilities. A common framework for verification and testing is, therefore, needed. We suggest several ways in which reference energies can be produced with free and open source software, either with non-self-consistent calculations with tabulated atomic densities or via self-consistent calculations with various program packages. The employed numerical parameters—especially the quadrature grid—need to be converged to guarantee a ≲0.1 μEh precision in the total energy, which is nowadays routinely achievable in fully numerical calculations. Moreover, as such sub-μEh level agreement can only be achieved when fully equivalent implementations of the DFA are used, the source code of the reference implementation should also be made available in any publication describing a new DFA. [ABSTRACT FROM AUTHOR]

The principle of the conventional ultrasound test states that the detectable voids cannot be smaller than the acoustic wavelength. However, by using effective medium approximation, the fraction of small voids can be estimated by the variation of the effective density. In this study, a non-contacting ultrasound-based porosity fraction mapping methodology is developed for estimated small voids in coal with long operating wavelength in air. This novel ultrasonic technique based on the mechanical properties of coal offers a rapid scan of the effective density mapping and distribution of void fraction over a large sample area, which overcame the limitation of small voids detection in the conventional ultrasound testing. [ABSTRACT FROM AUTHOR]

Recent coarse-grained (CG) models have often supplemented conventional pair potentials with potentials that depend upon the local density around each particle. In this work, we investigate the temperature-dependence of these local density (LD) potentials. Specifically, we employ the multiscale coarse-graining (MS-CG) force-matching variational principle to parameterize pair and LD potentials for one-site CG models of molecular liquids at ambient pressure. The accuracy of these MS-CG LD potentials quite sensitively depends upon the length-scale, rc, that is employed to define the local density. When the local density is defined by the optimal length-scale, r c * , the MS-CG potential often accurately describes the reference state point and can provide reasonable transferability across a rather wide range of temperatures. At ambient pressure, the optimal LD length-scale varies linearly with temperature over a very wide range of temperatures. Moreover, if one adopts this temperature-dependent LD length-scale, then the MS-CG LD potential appears independent of temperature, while the MS-CG pair potential varies linearly across this temperature range. This provides a simple means for predicting pair and LD potentials that accurately model new state points without performing additional atomistic simulations. Surprisingly, at certain state points, the predicted potentials provide greater accuracy than MS-CG potentials that were optimized for the state point. [ABSTRACT FROM AUTHOR]

Superadiabatic dynamical density functional theory (superadiabatic-DDFT), a first-principles approach based on inhomogeneous two-body correlation functions, is employed to investigate the response of interacting Brownian particles to time-dependent external driving. Predictions for the superadiabatic dynamics of the one-body density are made directly from the underlying interparticle interactions without the need for either adjustable fit parameters or simulation input. The external potentials we investigate have been chosen to probe distinct aspects of structural relaxation in dense, strongly interacting liquid states. Nonequilibrium density profiles predicted by the superadiabatic theory are compared with those obtained from both adiabatic DDFT and event-driven Brownian dynamics simulation. Our findings show that superadiabatic-DDFT accurately predicts the time-evolution of the one-body density. [ABSTRACT FROM AUTHOR]

We investigate the source of error in the Thomas–Fermi–von Weizsäcker (TFW) density functional relative to Kohn–Sham density functional theory (DFT). In particular, through numerical studies on a range of materials, for a variety of crystal structures subject to strain and atomic displacements, we find that while the ground state electron density in TFW orbital-free DFT is close to the Kohn–Sham density, the corresponding energy deviates significantly from the Kohn–Sham value. We show that these differences are a consequence of the poor representation of the linear response within the TFW approximation for the electronic kinetic energy, confirming conjectures in the literature. In so doing, we find that the energy computed from a non-self-consistent Kohn–Sham calculation using the TFW electronic ground state density is in very good agreement with that obtained from the fully self-consistent Kohn–Sham solution. [ABSTRACT FROM AUTHOR]

We present a Graphics Processing Unit (GPU)-accelerated version of the real-space SPARC electronic structure code for performing Kohn–Sham density functional theory calculations within the local density and generalized gradient approximations. In particular, we develop a modular math-kernel based implementation for NVIDIA architectures wherein the computationally expensive operations are carried out on the GPUs, with the remainder of the workload retained on the central processing units (CPUs). Using representative bulk and slab examples, we show that relative to CPU-only execution, GPUs enable speedups of up to 6× and 60× in node and core hours, respectively, bringing time to solution down to less than 30 s for a metallic system with over 14 000 electrons and enabling significant reductions in computational resources required for a given wall time. [ABSTRACT FROM AUTHOR]

A way to improve the accuracy of the spectral properties in density functional theory (DFT) is to impose constraints on the effective, Kohn–Sham (KS), local potential [J. Chem. Phys. 136, 224109 (2012)]. As illustrated, a convenient variational quantity in that approach is the "screening" or "electron repulsion" density, ρrep, corresponding to the local, KS Hartree, exchange and correlation potential through Poisson's equation. Two constraints, applied to this minimization, largely remove self-interaction errors from the effective potential: (i) ρrep integrates to N − 1, where N is the number of electrons, and (ii) ρrep ≥ 0 everywhere. In this work, we introduce an effective "screening" amplitude, f, as the variational quantity, with the screening density being ρrep = f2. In this way, the positivity condition for ρrep is automatically satisfied, and the minimization problem becomes more efficient and robust. We apply this technique to molecular calculations, employing several approximations in DFT and in reduced density matrix functional theory. We find that the proposed development is an accurate, yet robust, variant of the constrained effective potential method. [ABSTRACT FROM AUTHOR]

Discovery of a new oxidation state for an element expands its chemistry. A high oxidation state, such as +7, is rare for sp-block elements except for halogens. In this study, we determined that Te can attain a +7 oxidation state through the existence of a distorted octahedron (DOH) structure of TeCl6+ based on coupled cluster singles and doubles with perturbative triples calculations. We propose a new type of isomerization that resembles pseudorotation. The octahedron structure of TeF6+ bearing one elongated axial bond isomerizes to a DOH via an associated pseudorotation. [ABSTRACT FROM AUTHOR]

In two recent papers [A. D. Becke, J. Chem. Phys. 156, 214101 (2022) and A. D. Becke, J. Chem. Phys. 157, 234102 (2022)], we compared two Kohn–Sham density functionals based on physical modeling and theory with the best density-functional power-series fits in the literature. The best error statistics reported to date for a hybrid functional on the general main-group thermochemistry, kinetics, and noncovalent interactions (GMTKN55) chemical database of Goerigk et al. [Phys. Chem. Chem. Phys. 19, 32184 (2017)] were obtained. In the present work, additional second-order perturbation-theory terms are considered. The result is a 12-parameter double-hybrid density functional with the lowest GMTKN55 WTMAD2 "weighted total mean absolute deviation" error (1.76 kcal/mol) yet seen for any hybrid or double-hybrid density-functional approximation. We call it "DH23." [ABSTRACT FROM AUTHOR]

In this study, we prepared a multi-layer Tb–Fe/Pt/Tb–Fe wire to develop a multi-level magnetic memory. By applying current, magnetizations of the Tb–Fe layers were inversion symmetrically switched by spin– orbit torque (SOT) generated from the middle Pt layer. Measurements of SOT showed that its efficiency had opposite polarities in the top and bottom Tb–Fe layers. The switching current density of the top and bottom Tb–Fe layers shifted in opposite directions under a uniform perpendicular magnetic field. Because the perpendicular magnetic field broke the inversion symmetry of SOT generated from the middle Pt layer, it could be used to control the switching current. Our results prove that the additional uniform and perpendicular magnetic field can enhance the controllability of the magnetization state in case of multi-level SOT-induced magnetization switching. [ABSTRACT FROM AUTHOR]

In this article, we unravel the problem of interpreting the density scaling exponent for the polyatomic molecules representing the real van der Waals liquids. Our studies show that the density scaling exponent is a weighted average of the exponents of the repulsive terms of all interatomic interactions that occur between molecules, where the potential energy of a given interaction represents its weight. It implies that potential energy is a key quantity required to calculate the density scaling exponent value for real molecules. Finally, we use the well-known method for potential energy estimation and show that the density scaling exponent could be successfully predicted from the liquid structure for fair representatives of the real systems. [ABSTRACT FROM AUTHOR]

Semi-empirical quantum models such as Density Functional Tight Binding (DFTB) are attractive methods for obtaining quantum simulation data at longer time and length scales than possible with standard approaches. However, application of these models can require lengthy effort due to the lack of a systematic approach for their development. In this work, we discuss the use of the Chebyshev Interaction Model for Efficient Simulation (ChIMES) to create rapidly parameterized DFTB models, which exhibit strong transferability due to the inclusion of many-body interactions that might otherwise be inaccurate. We apply our modeling approach to silicon polymorphs and review previous work on titanium hydride. We also review the creation of a general purpose DFTB/ChIMES model for organic molecules and compounds that approaches hybrid functional and coupled cluster accuracy with two orders of magnitude fewer parameters than similar neural network approaches. In all cases, DFTB/ChIMES yields similar accuracy to the underlying quantum method with orders of magnitude improvement in computational cost. Our developments provide a way to create computationally efficient and highly accurate simulations over varying extreme thermodynamic conditions, where physical and chemical properties can be difficult to interrogate directly, and there is historically a significant reliance on theoretical approaches for interpretation and validation of experimental results. [ABSTRACT FROM AUTHOR]

In this research, hollow inorganic microsphere (Q-cel) reinforced unsaturated polyester composite is produced, and its thermophysical properties have been characterized. The thermal decomposition kinetics of the composite obtained at different heating rates and various compositions are modeled using artificial neural networks. Also, the production optimization of the polyester composite has been evaluated using response surface methodology. The study has been repeated for certain heating rates (5, 10, and 20 K/min). Activation energies of polyester composites have been calculated using thermogravimetric data and kinetic methods. Changes in activation energy during the thermal decomposition (4 wt.% Q-cel, 94 wt.% UP, 580–660 K, and 20 K/min) of the composite are compared using FWO (129.4 kJ/mol), KAS (127.6 kJ/mol), and CR (126.5 kJ/mol). According to the results, it is seen that the activation energy goes up as the temperature and Q-cel ratio by the mass increase. When the amount of the filler in the polyester composite increases, the thermal conductivity coefficient also rises. As well as, it is determined that as Q-cel ratio in the mixture raises, the density of the composite decreases and Shore D hardness goes up. A new and original composite has been produced with Qcel-reinforced unsaturated polyester. The density of the composite is low, its thermal stability is high, and its easy processability will provide a great convenience. Modeling the Qcel ratio of the composite with RSM and the activation energy with ANN have been provided fast, efficient and optimum results. With the composite obtained, both lightweight and thermally stable polymer materials will be produced. [ABSTRACT FROM AUTHOR]

The ability to manipulate the dimensions, areal density, and form of substrate-supported Au and Ag nanoparticles (NPs) is highly desirable for utilizing their plasmonic properties in biosensing, photovoltaics, and nanophotonic applications. The transformation of thin films into the substrate-supported nanostructures by solid-state dewetting (SSD), provides an avenue to manipulate the dimensional aspects of nanostructures simply and cost-effectively on a large scale. However, spontaneous agglomeration of the film produces randomly distributed and non-uniform nanostructures that must be controlled. Here, we have systematically studied the effect of annealing temperature, between 200 °C and 750 °C, on the dewetting morphology evolution of Au, Ag, and Au–Ag bilayer ultrathin films sputter deposited on the c -plane (0001) sapphire substrates. Regardless of the film thickness, Ag films dewet faster than Au films and produce spherical NPs, compared to faceted Au NPs, with broader size distribution. Whereas, by the SSD of Au–Ag bilayer ultrathin films, highly spherical and monodisperse AuAg bimetallic NPs can be fabricated. Furthermore, we have shown the possibility of fabricating the AuAg bimetallic NPs of varying compositions by adjusting the thickness of individual layers, thus enabling us to smoothly tune the spectral location of plasmonic resonance within the visible range. [ABSTRACT FROM AUTHOR]

Density has been a key focus in research on the urban dimensions of the COVID-19 pandemic. Much of this work has debated the role of density in infection rates. In contrast, we develop a comparison of the management of pandemic urbanism in two high density Asian cities with divergent pandemic experiences: Manila and Taipei. To pursue the comparison, we develop two conceptualisations of density: exposure density and networked density. Our approach allows us to examine the nature and consequences, especially for the urban poor, of different approaches to density in the pandemic, and to advance research on urban density. [ABSTRACT FROM AUTHOR]

FLACS with customized nuclear fragmentation patterns resulted in significantly less intraoperative phacoemulsification time, surgical time, and endothelial cell loss compared with conventional phacoemulsification for dense cataracts. Purpose: To compare the safety, effectiveness, and changes in endothelial cell density (ECD) after standard phacoemulsification and femtosecond laser-assisted cataract surgery (FLACS) in dense cataracts (Lens Opacities Classification System III grade 3.0 NO and above). Setting: Nethradhama Superspeciality Eye Hospital, Bangalore, India. Design: Prospective, randomized, comparative study. Method: 100 eyes of 100 patients were randomly assigned to either conventional phacoemulsification surgery (CPS) or FLACS (LENSAR Laser System) using predefined patterns of nuclear fragmentations. Measured outcomes included intraoperative phacoemulsification time, irrigation fluid volume, surgical time, and complication rates. ECD was evaluated at baseline, 2 weeks, and 6 months postoperatively. Results: The CPS group had significantly higher mean total phacoemulsification time (11.17 ± 6.5 seconds vs 8.03 ± 3.77 seconds), effective phacoemulsification time (6.14 ± 3.62 seconds vs 4.42 ± 2.07 seconds), and total surgical time (8.18 ± 2.36 minutes vs 7.11 ± 1.55 minutes) than the FLACS group (P <.001). Volume of irrigation fluid was comparable between the 2 groups (CPS, 36.7 ± 12.18 mL; FLACS, 38.64 ± 13.73 mL (P =.45). Mean corneal edema score and central corneal thickness values on postoperative day 1 were significantly higher for the CPS group. At 6 months, % ECD loss was significantly higher in the CPS group (16.08%) vs the FLACS group (12.8%) (P <.001). 3 eyes in the CPS group had wound burns of varying severity. Conclusions: FLACS with customized nuclear fragmentation patterns resulted in significantly less intraoperative phacoemulsification time, surgical time, and endothelial cell loss compared with conventional phacoemulsification when treating dense cataracts. Trial Registration Number: CTRI/2021/12/038887. [ABSTRACT FROM AUTHOR]

The driven-dissipative Langevin dynamics simulation is used to produce a two-dimensional (2D) dense cloud, which is composed of charged dust particles trapped in a quadratic potential. A 2D mesh grid is built to analyze the center-to-wall dust density. It is found that the local dust density in the outer region relative to that of the inner region is more nonuniform, being consistent with the feature of quadratic potential. The dependences of the global dust density on equilibrium temperature, particle size, confinement strength, and confinement shape are investigated. It is found that the particle size, the confinement strength, and the confinement shape strongly affect the global dust density, while the equilibrium temperature plays a minor effect on it. In the direction where there is a stronger confinement, the dust density gradient is bigger. [ABSTRACT FROM AUTHOR]

For a positive integer t ≥ 2 , let b t (n) denote the number of t-regular partitions of a nonnegative integer n. Motivated by some recent conjectures of Keith and Zanello, we establish infinite families of congruences modulo 2 for b 9 (n) and b 19 (n) . We prove some specific cases of two conjectures of Keith and Zanello on self-similarities of b 9 (n) and b 19 (n) modulo 2. For t ∈ { 6 , 10 , 14 , 15 , 18 , 20 , 22 , 26 , 27 , 28 } , Keith and Zanello conjectured that there are no integers A > 0 and B ≥ 0 for which b t (A n + B) ≡ 0 (mod 2) for all n ≥ 0 . We prove that, for any t ≥ 2 and prime ℓ , there are infinitely many arithmetic progressions A n + B for which ∑ n = 0 ∞ b t (A n + B) q n ≢ 0 (mod ℓ) . Next, we obtain quantitative estimates for the distributions of b 6 (n) , b 10 (n) and b 14 (n) modulo 2. We further study the odd densities of certain infinite families of eta-quotients related to the 7-regular and 13-regular partition functions. [ABSTRACT FROM AUTHOR]

Arithmetic quasidensities are a large family of real-valued set functions partially defined on the power set of $\mathbb {N}$ , including the asymptotic density, the Banach density and the analytic density. Let $B \subseteq \mathbb {N}$ be a nonempty set covering $o(n!)$ residue classes modulo $n!$ as $n\to \infty $ (for example, the primes or the perfect powers). We show that, for each $\alpha \in [0,1]$ , there is a set $A\subseteq \mathbb {N}$ such that, for every arithmetic quasidensity $\mu $ , both A and the sumset $A+B$ are in the domain of $\mu $ and, in addition, $\mu (A + B) = \alpha $. The proof relies on the properties of a little known density first considered by Buck ['The measure theoretic approach to density', Amer. J. Math. 68 (1946), 560–580]. [ABSTRACT FROM AUTHOR]

Many researchers have proposed numerous Bayesian predictive densities for Type-II censored data that is generated by ordered observations. However, their evaluations of predictive densities were insufficient because the Bayesian predictive density includes prior parameters, thus we suffer from the selection of the prior parameters. In this study, we consider two types of predictive densities, posterior predictive and plug-in, for observations from an exponential distribution of Type-II censored data. We discuss a suitable predictive density using the risk with the Kullback–Leibler loss function. In our setting, we consider a Gamma prior, which is a conjugate prior for mathematical tractability. We prove that the posterior predictive density with an improper Gamma prior provides the dominance of the posterior predictive density over the plug-in densities without depending on the selection of an unknown parameter in our setting. Finally, we show that the posterior predictive density outperforms the plug-in densities in terms of coverage probabilities for unobserved data by censoring in a simulation study. [ABSTRACT FROM AUTHOR]

This paper argues that rising household indebtedness is associated with the decline of organised labour. Over the last decades, the financial system is increasingly financing working-class households, and recent research shows that indebted employees become more risk-averse at the workplace on the fear of losing their job and defaulting. Thus, since union formation or participation is commonly punished with redundancy, rising household indebtedness is likely to be associated with the aggregate reduction in unionisation. This study examines this argument for a high-, a mid-, and low-unionisation economy over the period 1965–2018: Sweden, Japan, and South Korea, respectively. Regression analysis provides robust support in favour of this argument. The results also suggest that financial regulation and social norms about personal insolvency matter for the size of the effects of household debt on unionisation. [ABSTRACT FROM AUTHOR]

The thermal expansion coefficient of talc has been measured using a high-temperature thermal optical expansion apparatus over a temperature range of 296 to 1473 K. The results show a gradual increase in the thermal expansion coefficient between 296 and 1086 K, and a rapid and substantial increase between 1086 and 1316 K, but exhibit a decline trend between 1316 and 1473 K. At lower temperatures, changes in crystal structure are the primary mechanism governing thermal expansion; at higher temperatures, the dehydration phase transition and the resulting formation of cracks are the primary contributors to thermal expansion. The volume of talc exhibits a linear increase with temperature, described by the equation: . At high temperatures (573–1073 K), by fitting the expansion data to the Grüneisen thermal equation of state, bulk modulus K0​ = 47.3 ± 0.9 GPa, pressure derivative = 6.2 ± 0.4, cell volume V0​ = 904.5 ± 0.6 ų, and Debye temperature θ = 829.3 ± 0.6 K were obtained at 0 K. The presence of talc reduces the density of subduction zones, facilitating the exhumation of oceanic eclogites. [ABSTRACT FROM AUTHOR]

This paper studies density estimation and regression analysis with data observed on a general unit hypersphere and contaminated by measurement errors. We establish novel density and regression estimators, and study their asymptotic properties such as the rates of convergence and asymptotic normality. We also provide two types of asymptotic confidence intervals for both density and regression functions. One type is based on the asymptotic normality of their estimators and the other type is based on the empirical likelihood technique. We present practical details on the implementation of our method as well as simulation studies and real data analysis. [ABSTRACT FROM AUTHOR]

Isn't there something like an amount and density of horrific suffering whose discovery would make it irrational to think God exists? Use your imagination to think of worlds that are much, much, much worse than you think Earth is when it comes to horrific suffering. Isn't there some conceivable scenario which, if you were in it, would make you say 'Okay, okay. God doesn't exist, at least in the way we thought God was. We were wrong about that'? Pursuing this question leads to what I call the Problem of Absurd Evil. [ABSTRACT FROM AUTHOR]