Non-equilibrium Conditions Research Articles

Semi-infinite Simple Exclusion Process: From Current Fluctuations to Target Survival.

The symmetric simple exclusion process (SEP), where diffusive particles cannot overtake each other, is a paradigmatic model of transport in the single-file geometry. In this model, the study of currents has attracted a lot of attention, but so far most results are restricted to two geometries: (i)a finite system between two reservoirs, which does not conserve the number of particles but reaches a nonequilibrium steady state, and (ii)an infinite system which conserves the number of particles but never reaches a steady state. Here, we obtain an expression for the full cumulant generating function of the integrated current in the important intermediate situation of a semi-infinite system connected to a reservoir, which does not conserve the number of particles and never reaches a steady state. This results from the determination of the full spatial structure of the correlations, which we infer to obey the very same closed equation recently obtained in the infinite geometry and argue to be exact. Besides their intrinsic interest, these results allow us to solve two open problems: the survival probability of a fixed target in the SEP, and the statistics of the number of particles injected by a localized source.

Influence of Solid-Phase and Melt-Quenching Na3Fe2(PO4)3 Polycrystal Production Technology on Their Structure and Ionic Conductivity

This article studies the influence of solid-phase (type 1 samples) and melt-quenching (type 2 samples) technological modes of obtaining Na3Fe2(PO4)3 polycrystals on their structures and ion-conducting properties. α-Na3Fe2(PO4)3 polycrystals of the 1st type are formed predominantly under an isothermal firing regime, and the synthesis of the 2nd type is carried out under sharp temperature gradient conditions, contributing to the formation of glassy precursors possessing a reactive and deformed structure, in which the crystallization of crystallites occurs faster than in precursors obtained under isothermal firing. The elemental composition of α-Na3Fe2(PO4)3 type 2 polycrystals is maintained within the normal range despite the sharp non-equilibrium thermodynamic conditions of synthesis. The microstructure of the type 1 Na3Fe2(PO4)3 polycrystals is dominated by chaotically arranged crystallites of medium (7–10 μm) and large (15–35 μm) sizes, while the polycrystals of type 2 are characterized by the preferential formation of small (3–4 μm) and medium (7–10 μm) crystallites, causing uniaxial deformations in their structure, which contribute to a partial increase in their symmetry. The advantage of type 2 polycrystals is that they have higher density and conductivity and are synthesized faster than type 1 samples by a factor of 4. The article also considers the issues of crystallization in a solid-phase precursor from the classical point of view, i.e., the process of the formation of small solid-phase nuclei in the metastable phase and their growth to large particles due to association with small crystallites using phase transitions. Possible variants and models of crystallite growth in Na3Fe2(PO4)3 polycrystals, as well as distinctive features of crystallization between two types of samples, are discussed.

Membrane Adsorption Enhances Translocation of Antimicrobial Peptide Buforin 2.

Despite ongoing research on antimicrobial peptides (AMPs) and cell-penetrating peptides (CPPs), their precise translocation mechanism remains elusive. This includes Buforin 2 (BF2), a well-known AMP, for which spontaneous translocation across the membrane has been proposed but a high barrier has been calculated. Here, we used computer simulations to investigate the effect of a nonequilibrium situation where the peptides are adsorbed on one side of the lipid bilayer, mimicking experimental conditions. We demonstrated that the asymmetric membrane adsorption of BF2 enhances its translocation across the lipid bilayer by lowering the energy barrier by tens of kJ mol-1. We showed that asymmetric membrane adsorption also reduced the free energy barrier of lipid flip-flop but remained unlikely even at BF2 surface saturation. These results provide insight into the driving forces behind membrane translocation of cell-penetrating peptides in nonequilibrium conditions, mimicking experiments.

Machine learning assisted sorting of active microswimmers.

Active matter systems, being in a non-equilibrium state, exhibit complex behaviors, such as self-organization, giving rise to emergent phenomena. There are many examples of active particles with biological origins, including bacteria and spermatozoa, or with artificial origins, such as self-propelled swimmers and Janus particles. The ability to manipulate active particles is vital for their effective application, e.g., separating motile spermatozoa from nonmotile and dead ones, to increase fertilization chance. In this study, we proposed a mechanism-an apparatus-to sort and demix active particles based on their motility values (Péclet number). Initially, using Brownian simulations, we demonstrated the feasibility of sorting self-propelled particles. Following this, we employed machine learning methods, supplemented with data from comprehensive simulations that we conducted for this study, to model the complex behavior of active particles. This enabled us to sort them based on their Péclet number. Finally, we evaluated the performance of the developed models and showed their effectiveness in demixing and sorting the active particles. Our findings can find applications in various fields, including physics, biology, and biomedical science, where the sorting and manipulation of active particles play a pivotal role.

Metastable phases of Ag–Si: amorphous Si and Ag-nodule mediated bonding

Metastable phases such as supersaturated solid solutions, supercooling, and amorphous phases are well-known in metallurgy. They are often composed in non-equilibrium states and can be transformed into a stable phase by overcoming an energy barrier with driving forces. Particularly, it has been widely used for material strengthening and heterogeneous nucleation of precipitates in solids is mainly induced by heat treatments for supersaturated solid solutions. However, little is known about the metastable phases of the Ag–Si alloy, although it is a well-known simple binary eutectic alloy. Here, we show that the metastable phases composed of amorphous Si and supersaturated Ag solid solution are induced by the eutectic reaction under rapid cooling of Ag–Si. Furthermore, the solute Si in the Ag matrix reacts with oxygen to precipitate Ag by-products, which grow as nodules. The Ag nodules have high crystallinity and robust interfacial structures, and the nodule growth leads to the formation of cross-links between the Ag–Si particles. We also demonstrate the Ag nodule-mediated bonding where the rapidly cooled Ag–Si ribbon is directly used as a bonding medium, indicating the possibility of using it as a high-temperature bonding material with low-temperature processes.

Polymerization-induced Chiral Self-assembly for the In situ Construction, Modulation, Amplification and Applications of Asymmetric Suprastructures.

In the polymerization-induced chiral self-assembly (PICSA) process, chiral functional monomers undergo spontaneous supramolecular self-assembly and asymmetric stacking during living polymerization, leading to the in situ generation of chiroptical polymer assemblies characterized by diverse morphologies. The PICSA strategy facilitates precise control and manipulation of both non-covalent supramolecular helices and covalent macromolecular helices within aggregated cores, thereby driving significant advancements in fields such as chiral recognition materials, asymmetric catalysts, nonlinear optical materials, and ferroelectric liquid crystals (LC). This minireview summarizes recent developments in the in situ chiroptical construction and modulation associated with the PICSA methodology. Furthermore, it seeks to elucidate emerging PICSA systems founded on various living polymerization mechanisms, exploring hierarchical chirality transfer processes and the pathway complexities in both equilibrium and non-equilibrium conditions. This minireview also presents several illustrative examples that demonstrate the practical applications of chiral polymer materials synthesized through the PICSA approach, thereby illuminating future opportunities in this innovative field.

Thermodynamic approach for designing processing routes of 4Mn quenching and partitioning steel

AbstractThe study addresses the design and optimization of chemical composition and processing routes of new quenching and partitioning medium-Mn alloy using theoretical and experimental approaches. The thermodynamic calculations using Thermo-Calc and JMatPro software were carried out to characterize the influence of Mn, Si and Al contents on cementite formation and precipitation processes. The evolution of individual phases as a function of temperature under thermodynamic equilibrium conditions was estimated. The investigations included the determination of continuous cooling transformation (CCT) and the time–temperature transformation (TTT) diagrams of a model 4Mn alloy. The calculated equilibrium diagrams were compared with the experimental diagrams determined using dilatometric tests. Microstructural observations were carried out to verify the results of dilatometric measurements. The results of thermodynamic calculations and experimental tests showed the moderate agreement. It is related to the inaccuracy of currently available models in the used software and/or non-equilibrium conditions of experimental tests.

Enantiomer Recognition by the Difference in Adsorption Rates on the Surfaces of Chiral Crystals.

The chirality of biopolymers remains one of the mysteries of Life. For such objects, the phenomenon of supramolecular chirality (SMC) is vital. Enantiomers can be recognized by the adsorption on surfaces with SMC. However, the mechanisms of such chiral recognition are still unknown. In this work, the adsorption kinetics of menthol test enantiomers on the surfaces of γ-glycine and NiSO4•6H2O chiral crystals was studied. It was found that the difference in adsorption was observed in nonequilibrium state more often than in equilibrium. If the enantioselectivity in equilibrium state was observed, the enantioselectivity coefficient α at nonequilibrium conditions was higher. The maximum α in nonequilibrium state was 2.44 for γ-glycine crystals and 2.12 for NiSO4•6H2O crystals. Even if no differences in adsorption were observed under adsorption-desorption equilibrium conditions, a significant enantioselectivity at nonequilibrium conditions was found. This has proved the possibility of chiral recognition on surfaces with SMC by the differences in adsorption rates. Such novel chiral recognition mechanism can provide enhanced enantioselectivity in adsorption, catalysis, chromatographic separation, and chemical sensing.

Q-triplet characterization of atmospheric time series at Antofagasta: A missing values problem

Abstract Located in northern Chile (23.7°S, 70.4°W), Antofagasta has an exceptionally arid and stable climate characterized by minimal precipitation and consistent weather patterns. Nevertheless, despite these climate conditions being meaningful for several research and practical applications, our understanding of weather dynamics remains limited. The available meteorological data from 1969 to 2016 is analogical, which presents a significant challenge to analyze because these records are riddled with missing values, some measurements were taken at irregular measuring intervals, making it an interesting puzzle to grasp the Antofagasta’s climate scenario. To overcome this issue, we present a comprehensive statistical analysis of atmospheric temperature, pressure, and humidity time series. Our analytical approach involves the q-triplet calculation method, serving as a powerful tool to identify distinctive behavior within systems under non-equilibrium states. Our results suggest that, in general, the q-triplet values satisfy the condition q sens < 1 < q stat < q rel, a pattern that has been observed in previous studies.

Thermal stability of electron beam welded AlCoCrFeNi2.1 alloy

Abstract AlCoCrFeNi2.1 alloy, which belongs to the group of eutectic high-entropy alloys (EHEAs), possesses a combination of increased strength and ductility. It should retain these properties over a wide temperature range due to the high entropy effect of the system. At the same time, eutectic alloys are generally considered to have good castability, which increases the possibility of casting the alloy in larger volumes. One of the processes, that the alloy does not avoid when applied in industry, are the various joining techniques including electron beam welding. The weld area is often in a non-equilibrium state, which increases the risk of failure during operation. The paper therefore discusses the stability of the microstructure and mechanical properties of AlCoCrFeNi2.1 alloy when exposed to short-term elevated temperatures. The material heated at 900 °C for 1 h in a vacuum furnace was observed using light and electron microscopy, analyzed for chemical and phase composition and finally subjected to HV0.1 hardness measurement and tensile strength test. The resulting condition was compared with the welded joint before exposure to elevated temperature. The microstructure of the weld was formed by a fine lamellar eutectic over the entire observed area. EBSD analysis confirmed the presence of a combination of FCC and BCC phases. The material hardness reached an average value of 370 HV0.1. Maximum tensile strength of the weld joint was measured at 944 MPa with the corresponding displacement of the crosshead 6.1 mm. The welded joint demonstrated sufficient stability and the ability to withstand short-term severe elevated temperature conditions.

Periodic Coronal Rain Driven by Self-consistent Heating Process in a Radiative Magnetohydrodynamic Simulation

The periodic coronal rain and in-phase radiative intensity pulsations have been observed in multiple wavelengths in recent years. However, due to the lack of three-dimensional coronal magnetic fields and thermodynamic data in observations, it remains challenging to quantify the coronal heating rate that drives the mass cycles. In this work, based on the MURaM code, we conduct a three-dimensional radiative magnetohydrodynamic simulation spanning from the convective zone to the corona, where the solar atmosphere is heated self-consistently through dissipation resulting from magnetoconvection. For the first time, we model the periodic coronal rain in an active region. With a high spatial resolution, the simulation well resembles the observational features across different extreme-ultraviolet wavelengths. These include the realistic interweaving coronal loops, periodic coronal rain, and periodic intensity pulsations, with two periods of 3.0 hr and 3.7 hr identified within one loop system. Moreover, the simulation allows for a detailed three-dimensional depiction of coronal rain on small scales, revealing adjacent shower-like rain clumps ∼500 km in width and showcasing their multithermal internal structures. We further reveal that these periodic variations essentially reflect the cyclic energy evolution of the coronal loop under thermal nonequilibrium state. Importantly, as the driver of the mass circulation, the self-consistent coronal heating rate is considerably complex in time and space, with hour-level variations in 1 order of magnitude, minute-level bursts, and varying asymmetry reaching ten times between footpoints. This provides an instructive template for the ad hoc heating function and further enhances our understanding of the coronal heating process.

Radiative heat transfer analysis of a concave porous fin under the local thermal non-equilibrium condition: application of the clique polynomial method and physics-informed neural networks

Radiative heat transfer analysis of a concave porous fin under the local thermal non-equilibrium condition: application of the clique polynomial method and physics-informed neural networks

Effect of laser power density on formation of oxide particles during ablation of metallic bismuth in atmospheric air

Purposeful synthesis of bismuth oxide nanoparticles (NPs) of various crystal modifications is important for biomedicine, photocatalysis and other applications. In this work, pulsed laser ablation of a metallic Bi target in atmospheric air is used to obtain β-Bi2O3 NPs. The effect of the Nd:YAG laser radiation power density (1064 nm, 7 ns) in the range of 0.1–1.2 GW/cm2 on the features of formation of NPs under nonequilibrium conditions is studied, for which the spectra of laser-induced plasma are recorded and analyzed, the plasma composition is determined, and the temperature of the plasma plume is estimated. The NPs are comprehensively characterized using TEM, XRD, FTIR, Raman, and UV–Vis spectroscopies, and electrophoretic light scattering, which make it possible to determine their morphology, crystal structure, chemical composition, and optical properties. The photocatalytic activity of the resulting nanopowders in the Rhodamine B dye decomposition reaction is assessed.

Long-range velocity correlations from active dopants

Active matter systems display collective behaviors that are impossible in thermodynamic equilibrium. One such feature, observed in in dense active matter systems is the appearance of long-range velocity correlations without explicit aligning interaction. However, the conditions for the appearance of these correlations remain largely unexplored. Here we show that such long-range velocity correlations can also be generated in a dense athermal passive system by the inclusion of a very small fraction of active Brownian particles. We develop a continuum theory to explain the emergence of velocity correlations generated via such active dopants. We validate the predictions for the effects of magnitude and persistence time of the active force and the area fractions of active and passive particles using extensive Brownian dynamics simulation of a canonical active-passive mixture. Our work decouples the roles that density and activity play in generating long-range velocity correlations in such exotic non-equilibrium steady states.

Revisiting Numerical Solutions of Weakly Bound Noble Gases' Vibrational Energy Levels Modeled by the Improved Lennard-Jones Potential.

We revisit the numerical solutions of vibrational eigenstates of weakly bound homonuclear and heteronuclear noble gas pairs by applying a Fortran program based on the Numerov method. The harmonic, Lennard-Jones (LJ), Morse, Tang-Toennies (TT), and Improved Lennard-Jones (ILJ) potential models have been implemented to represent the potential energy curves (PECs). The obtained vibrational energies spectrum was tested on the experimental data and accurate ab initio calculations at CCSD(T)/CBS level. The vibrational eigenvalues and eigenfunctions can be reproduced accurately within the ILJ potential model. Moreover, considering the calculated lifetime of van der Waals (vdW) complexes, the implementation of ILJ rather than standard LJ potential model has a significant impact on the systems dynamics by providing more representative atomic trajectories when the function is incorporated in force fields for molecular dynamics (MD) simulations. Overall, the ILJ function is the best suited potential model for the representation of vibrational motions and the determination of vibrational energy levels of weakly bound systems, both at equilibrium and non-equilibrium conditions.

Impact of Thickness of Pd/Cu Membrane on Performance of Biogas Dry Reforming Membrane Reactor Utilizing Ni/Cr Catalyst

The present study pays attention to biogas dry reforming for the purpose of producing H2. It is known that biogas contains approximately 40 vol% CO2, causing a decrease in the efficiency of power generation due to its lower heating value compared to natural gas, i.e., CH4. We suggest a hybrid system composed of a biogas dry reforming membrane reactor and a high-temperature fuel cell, i.e., a solid oxide fuel cell (SOFC). Since biogas dry reforming is an endothermic reaction, we adopt a membrane reactor, controlled by providing a non-equilibrium state via H2 separation from the reaction site. The purpose of the present study is to understand the effect of the thickness of the Pd/Cu membrane on the performance of the biogas dry reforming membrane reactor with a Pd/Cu membrane as well as a Ni/Cr catalyst. The impact of the reaction temperature, the molar ratio of CH4:CO2 and the differential pressure between the reaction chamber and the sweep chamber on the performance of the biogas dry reforming membrane reactor with the Pd/Cu membrane as well as the Ni/Cr catalyst was investigated by changing the thickness of the Pd/Cu membrane. It was revealed that we can obtain the highest concentration of H2, of 122,711 ppmV, for CH4:CO2 = 1:1 at a reaction temperature of 600 °C and a differential pressure of 0 MPa and using a Pd/Cu membrane with a thickness of 40 μm. Under these conditions, it can be concluded that the differential pressure of 0 MPa provides benefits for practical applications, especially since no power for H2 separation is necessary. Therefore, the thermal efficiency is improved, and additional equipment, e.g., a pump, is not necessary for practical applications.

Numerical simulations of temperature anisotropy instabilities stimulated by suprathermal protons

The new in situ measurements of the Solar Orbiter mission contribute to the knowledge of the suprathermal populations in the solar wind, especially of ions and protons whose characterization, although still in the early phase, seems to suggest a major involvement in the interaction with plasma wave fluctuations. Recent studies point to the stimulating effect of suprathermal populations on temperature anisotropy instabilities in the case of electrons already being demonstrated in theory and numerical simulations. Here, we investigate anisotropic protons, addressing the electromagnetic ion-cyclotron (EMIC) and the proton firehose (PFH) instabilities. Suprathermal populations enhance the high-energy tails of the Kappa velocity (or energy) distributions measured in situ, enabling characterization by contrasting to the quasi-thermal population in the low-energy (bi-)Maxwellian core. We use hybrid simulations to investigate the two instabilities (with ions or protons as particles and electrons as fluid) for various configurations relevant to the solar wind and terrestrial magnetosphere. The new simulation results confirm the linear theory and its predictions. In the presence of suprathermal protons, the wave fluctuations reach increased energy density levels for both instabilities and cause faster and/or deeper relaxation of temperature anisotropy. The magnitude of suprathermal effects also depends on each instability's specific (initial) parametric regimes. These results further strengthen the belief that wave-particle interactions govern space plasmas. These provide valuable clues for understanding their dynamics, particularly the involvement of suprathermal particles behind the quasi-stationary non-equilibrium states reported by in situ observations.

Advantages of Ultrathin AlN/GaN/AlN Quantum Wells for Excitonic Population Distribution and Transition Features Studied by Phononic–Excitonic–Radiative Model

Excitons are expected to be a high‐efficiency emission source in UV light‐emitting devices. However, the damping of the excitonic laser oscillation has been reported under conditions where the excitonic states are expected to be populated in the conventional theory. In order to understand the exciton dynamics under the thermal nonequilibrium state, a theoretical model including various energy species in semiconductors such as electrons, phonons, and photons is required. Herein, a 2D phononic–excitonic–radiative model is constructed to analyze the exciton dynamics in a 2D system. 2D excitons with four principal quantum number states and the continuum in the lowest energy level of the AlN/GaN/AlN quantum wells are considered. It is found that the 2D phonon significantly augments the excitation transition rate. When the high recombination rate corresponding to stimulated emission is considered, the exciton binding energy of 108 meV is not enough to reduce the population in the high‐order discreet states and the continuum states, while the binding energy of 215 meV corresponding to the one monolayer GaN has an advantage of reducing these populations. The analysis of population flux has an advantage in discussing the increase in the kinetic energy transfer to the 1S exciton.

Non-thermal plasma-catalytic processes for CO2 conversion toward circular economy: fundamentals, current status, and future challenges.

Practical and energy-efficient carbon dioxide (CO2) conversion to value-added and fuel-graded products and transitioning from fossil fuels are promising ways to cope with climate change and to enable the circular economy. The carbon circular economy aims to capture, utilize, and minimize CO2 emissions as much as possible. To cope with the thermodynamic stability and highly endothermic nature of CO2 conversion via conventional thermochemical process, the potential application of non-thermal plasma (NTP) with the catalyst, i.e., the hybrid plasma catalysis process to achieve the synergistic effects, in most cases, seems to promise alternatives under non-equilibrium conditions. This review focuses on the NTP fundamentals and comparison with conventional technologies. A critical review has been conducted on the CO2 reduction with water (H2O), methane (CH4) reduction with CO2 to syngas (CO + H2), CO2 dissociation to carbon monoxide (CO), CO2 hydrogenation, CO2 conversion to organic acids, and one-step CO2-CH4 reforming to the liquid chemicals. Finally, future challenges are discussed comprehensively, indicating that plasma catalysis has immense investigative areas.

Non-equilibrium self-assembly for living matter-like properties.

The soft and wet machines of life emerged as the spatially enclosed ensemble of biomolecules with replicating capabilities integrated with metabolic reaction cycles that operate at far-from-equilibrium. A thorough step-by-step synthetic integration of these elements, namely metabolic and replicative properties all confined and operating far-from-equilibrium, can set the stage from which we can ask questions related to the construction of chemical-based evolving systems with living matter-like properties - a monumental endeavour of systems chemistry. The overarching concept of this Review maps the discoveries on this possible integration of reaction networks, self-reproduction and compartmentalization under non-equilibrium conditions. We deconvolute the events of reaction networks and transient compartmentalization and extend the discussion towards self-reproducing systems that can be sustained under non-equilibrium conditions. Although enormous challenges lie ahead in terms of molecular diversity, information transfer, adaptation and selection that are required for open-ended evolution, emerging strategies to generate minimal metabolic cycles can extend our growing understanding of the chemical emergence of the biosphere of Earth.