Thermodynamic Equilibrium Conditions Research Articles

(Invited) Role of Solvent Exchange Dynamics in the Performance of Metal Anode

Designing resilient and high performing batteries is a critical component in decarbonizing our economy. Facilitating the uniform and fully reversible deposition of the metal anode remains a major roadblock in realizing many battery chemistries, including multivalent batteries. The intrinsic electrolyte properties, such as the solvation phenomena of the working cation, have widely known as critical control factor to facilitate the reversible, dendrite-free, and efficient charge transfer at metal anode. However, predominant work in this field is focused on static view of solvation phenomena, such as structure and composition of first sphere solvation shell, although the solvation process is highly dynamic and driven by solvent and/or anion exchange processes driven by thermodynamic and kinetic equilibrium conditions. In this presentation, we will discuss how exchange, conformal, and re-organizational dynamics of electrolyte constituents around divalent metal cations affects the performance metrics of metal anode based batteries, namely (1) the ionic diffusivity and emerging conductivity of the bulk electrolyte; (2) the de/re-solvation processes of metal cations and emergent overpotential; and (3) the SEI evolution and emerging interfacial impedance. Through this study, we aim to generalize the strategies for designing new electrolyte systems for high-performance batteries by recognizing and regulating the critical role of solvation dynamics of working cations.

Energetic driving force for LHCII clustering in plant membranes.

Plants capture and convert solar energy in a complex network of membrane proteins. Under high light, the luminal pH drops and induces a reorganization of the protein network, particularly clustering of the major light-harvesting complex (LHCII). While the structures of the network have been resolved in exquisite detail, the thermodynamics that control the assembly and reorganization had not been determined, largely because the interaction energies of membrane proteins have been inaccessible. Here, we describe a method to quantify these energies and its application to LHCII. Using single-molecule measurements, LHCII proteoliposomes, and statistical thermodynamic modeling, we quantified the LHCII-LHCII interaction energy as ~-5 kBT at neutral pH and at least -7 kBT at acidic pH. These values revealed an enthalpic thermodynamic driving force behind LHCII clustering. Collectively, this work captures the interactions that drive the organization of membrane protein networks from the perspective of equilibrium statistical thermodynamics, which has a long and rich tradition in biology.

Spatial evolution and temporal stability of hydrothermal processes at sediment-covered spreading centers: Constraints from Guaymas Basin, Gulf of California

The Guaymas Basin, Gulf of California is a hydrothermally active sediment-covered oceanic spreading center in the early stages of rifting. Hot-spring fluids were collected from its southern trough in 1998, 2003, and 2008 and analyzed for the concentration and isotopic composition of organic and inorganic aqueous species to assess subseafloor geochemical processes. Fluids discharged from the seafloor through hydrothermal edifices with measured temperatures of 91 to 317 °C. In general, fluids exiting larger structures were characterized by higher temperatures than fluids venting from smaller structures. Measured pH (25 °C) ranged from 5.7 to 7.1. Endmember fluids were characterized by near-zero concentrations of Mg and SO4, depletions in Na, and enrichments in K, Ca, and Cl relative to seawater, reflecting extensive interaction with sediment during circulation. Thermal maturation of sedimentary organic matter resulted in the addition of abundant ΣNH4+, ΣCO2, CH4, short-chain n-alkanes, and carboxylic acids to solution. Organic compounds added to fluids during recharge pass through high temperature deep-seated reaction zones and reach high levels of thermal maturity while others may be added by entrainment of lower temperature sedimentary pore fluids in hydrothermal upflow zones.The relative abundance of many organic compounds mobilized during hydrothermal alteration is consistent with metastable states of thermodynamic equilibrium that likely record subseafloor temperature conditions. The isotope composition of low molecular weight hydrocarbons and elevated concentrations of dissolved Cl suggest that temperatures may have exceeded the two-phase boundary for seawater and subsequently cooled before discharging at the seafloor. Periods of high temperature fluid-sediment or fluid-rock interaction followed by cooling may provide a mechanism for the aqueous mobilization and concentration of sulfide-forming metals in subseafloor mineral deposits. Fluid compositions have remained constant at the southern trough of Guaymas Basin for at least 26 years, indicating decadal stability in the physical and chemical conditions in subseafloor environments as well as the km-scale regional recharge zones containing unaltered sediment.

Experimental Study on the Temporal Evolution Parameters of Laser–Produced Tin Plasma under Different Laser Pulse Energies for LPP–EUV Source

The laser–produced plasma extreme ultraviolet (LPP–EUV) source is the sole light source currently available for commercial EUVL (extreme ultraviolet lithography) machines. The plasma parameters, such as the electron temperature and electron density, affect the conversion efficiency (CE) of extreme ultraviolet radiation and other critical parameters of LPP–EUV source directly. In this paper, the optical emission spectroscopy (OES) was employed to investigate the time–resolved plasma parameters generated by an Nd:YAG laser irradiation on a planar tin target. Assuming that the laser–produced tin plasma satisfies the local thermodynamic equilibrium (LTE) condition, the electron temperature and electron density of the plasma were calculated by the Saha–Boltzmann plot and Stark broadening methods. The experimental results revealed that during the early stage of plasma formation (delay time < 50 ns), there was a significant presence of continuum emission. Subsequently, the intensity of the continuum emission gradually decreased, while line spectra emerged and became predominant at a delay time of 300 ns. In addition, the evolution trend of plasma parameters, with the incident laser pulse energy set at 300 mJ, was characterized by a rapid initial decrease followed by a gradual decline as the delay time increased. Furthermore, with an increase in the incident laser pulse energy from 300 mJ to 750 mJ, the electron temperature and electron density of laser–produced tin plasma exhibiting a monotonically showed increasing trend at the same delay time.

Nonequilibrium liquid-vapor interfaces: Linear and nonlinear descriptions.

While it is often assumed that liquid-vapor interfaces in nonequilibrium processes are in states of local thermodynamic equilibrium, this might not be the case for strong deviations from equilibrium. Clausius-Clapeyron equations for bulk properties yield a consistently defined temperature of the interface that is close to the liquid bulk temperature. The alternative interface temperature defined through the surface tension will be different for stronger nonequilibrium processes. Structural variables are introduced to extend the thermodynamic description of interfaces to a wider range of processes. Interfacial resistivities will depend on interface temperature as well as mass and heat flux through the interface.

A statistical mechanics framework for constructing nonequilibrium thermodynamic models

Abstract Far-from-equilibrium phenomena are critical to all natural and engineered systems, and essential to biological processes responsible for life. For over a century and a half, since Carnot, Clausius, Maxwell, Boltzmann, and Gibbs, among many others, laid the foundation for our understanding of equilibrium processes, scientists and engineers have dreamed of an analogous treatment of nonequilibrium systems. But despite tremendous efforts, a universal theory of nonequilibrium behavior akin to equilibrium statistical mechanics and thermodynamics has evaded description. Several methodologies have proved their ability to accurately describe complex nonequilibrium systems at the macroscopic scale, but their accuracy and predictive capacity is predicated on either phenomenological kinetic equations fit to microscopic data or on running concurrent simulations at the particle level. Instead, we provide a novel framework for deriving stand-alone macroscopic thermodynamic models directly from microscopic physics without fitting in overdamped Langevin systems. The only necessary ingredient is a functional form for a parameterized, approximate density of states, in analogy to the assumption of a uniform density of states in the equilibrium microcanonical ensemble. We highlight this framework’s effectiveness by deriving analytical approximations for evolving mechanical and thermodynamic quantities in a model of coiled-coil proteins and double-stranded DNA, thus producing, to the authors’ knowledge, the first derivation of the governing equations for a phase propagating system under general loading conditions without appeal to phenomenology. The generality of our treatment allows for application to any system described by Langevin dynamics with arbitrary interaction energies and external driving, including colloidal macromolecules, hydrogels, and biopolymers.

Biological thermodynamics: Ervin Bauer and the unification of life sciences and physics

Biological systems operate toward the maximization of their self-maintenance and adaptability. This is achieved through the establishment of robust self-maintaining configurations acting as attractors resistant to external and internal perturbations. Ervin Bauer (1890–1938) was the first who formulated this essential thermodynamic constraint in the operation of biological systems, which he defined as the stable non-equilibrium state. The latter appears as the basic attractor relative to which biological organization is established. The stable non-equilibrium state represents a generalized cell energy status corresponding to efficient spatiotemporal organization of the fluxes of matter and energy and constantly reproducing the conditions of self-maintenance of metabolism and controlling the rates of major metabolic fluxes that follow thermodynamically and kinetically defined computational principles. This state is realized in the autopoietic structures having closed loops of causation based on the operation of biological codes. The principle of thermodynamic buffering determines the conditions for optimization of the fluxes of load and consumption in metabolism establishing the conditions of metabolic stable non-equilibrium. In developing and evolving biological systems, the principle of stable non-equilibrium is transformed into the principle of increasing external work, which is grounded in the hyper-restorative non-equilibrium dynamics. Bauer's concept of the stable non-equilibrium state puts thermodynamics into the frames of the internal biological causality governing self-maintenance and development of living systems. It can be defined as a relational theory of biological thermodynamics since the standard to which it refers represents the actual biological function rather than the abstract state of thermodynamic equilibrium.

Stability of nanoparticle laden aerosol liquid droplets.

We develop a model for the thermodynamics and evaporation dynamics of aerosol droplets of a liquid, such as water, surrounded by gas. When the temperature and the chemical potential (or equivalently the humidity) are such that the vapor phase is in the thermodynamic equilibrium state, then, of course, droplets of the pure liquid evaporate over a relatively short time. However, if the droplets also contain nanoparticles or any other non-volatile solute, then the droplets can become thermodynamically stable. We show that the equilibrium droplet size depends strongly on the amount and solubility of the nanoparticles within, i.e., on the nature of the particle interactions with the liquid and, of course, also on the vapor temperature and chemical potential. We develop a simple thermodynamic model for such droplets and compare predictions with results from a lattice density functional theory that takes as input the same particle interaction properties, finding very good agreement. We also use dynamical density functional theory to study the evaporation/condensation dynamics of liquid from/to droplets as they equilibrate with the vapor, thereby demonstrating droplet stability.

Nanoarchitectonics on Electrosynthesis and Assembly of Conjugated Metallopolymers.

In contrast to edge-on and face-on orientations, end-on uniaxial conjugated polymers have the theoretical possibility of providing a macroscopic crystalline film. However, their fabrication is insurmountable due to sluggishly thermodynamic equilibrium states. Herein, we report the programmatic pathway to fabricate nanoarchitectonics on end-on uniaxial conjugated metallopolymers by surface-initiated simultaneous electrosynthesis and assembly. Self-assembled monolayer (SAM) with bottom-up oriented electroactive molecules as a temple allows orientation, stacking, and reactive addition of monomers triggered by switching alternative redox reactions as well as crystallization of small molecules. Repeating the same reaction can repair the unreactive site on the SAM and dynamically and statistically ensure maximum iterative coverage with ideal linear coefficients between optical or electrical responses and iterative times. The resulting nanoarchitectonics on uniaxially assembled end-on polymers over centimeter-sized areas have a subnanometer-uniform morphology and exhibit ultrahigh modulus as well as an inorganic indium tin oxides and the highest conductance among conjugated molecular monolayers. Their memristive devices provide quantitative electrical and optical responses as a function of molecular length, bias, and iterative junctions. Precise processing of nanoarchitectonics as an electrically assisted assembly or printing technique can present sophisticated optoelectric functions and dimensional batch-to-batch consistency for micro-sized organic materials and electronics.

Nanoarchitectonics on Electrosynthesis and Assembly of Conjugated Metallopolymers

AbstractIn contrast to edge‐on and face‐on orientations, end‐on uniaxial conjugated polymers have the theoretical possibility of providing a macroscopic crystalline film. However, their fabrication is insurmountable due to sluggishly thermodynamic equilibrium states. Herein, we report the programmatic pathway to fabricate nanoarchitectonics on end‐on uniaxial conjugated metallopolymers by surface‐initiated simultaneous electrosynthesis and assembly. Self‐assembled monolayer (SAM) with bottom‐up oriented electroactive molecules as a temple allows orientation, stacking, and reactive addition of monomers triggered by switching alternative redox reactions as well as crystallization of small molecules. Repeating the same reaction can repair the unreactive site on the SAM and dynamically and statistically ensure maximum iterative coverage with ideal linear coefficients between optical or electrical responses and iterative times. The resulting nanoarchitectonics on uniaxially assembled end‐on polymers over centimeter‐sized areas have a subnanometer‐uniform morphology and exhibit ultrahigh modulus as well as an inorganic indium tin oxides and the highest conductance among conjugated molecular monolayers. Their memristive devices provide quantitative electrical and optical responses as a function of molecular length, bias, and iterative junctions. Precise processing of nanoarchitectonics as an electrically assisted assembly or printing technique can present sophisticated optoelectric functions and dimensional batch‐to‐batch consistency for micro‐sized organic materials and electronics.

Atomistic simulations and machine learning of solute grain boundary segregation in Mg alloys at finite temperatures

Understanding solute segregation thermodynamics is the first step in investigating grain boundary (GB) properties, such as strong yttrium (Y) effects on grain growth and texture evolution in micro-scale polycrystalline magnesium (Mg) alloys. To estimate the average GB segregation behavior in low-solute-concentration Mg alloys (e.g., 2 at.% Y), a state-of-the-art spectral approach is applied based on a per-site segregation energy spectrum for Y solute atoms at zero K obtained from molecular statistics (MS) simulations of ∼104 GB sites in Mg symmetric tilt GBs (STGBs). Although selected MS simulation results are consistent with verification by density functional theory (DFT) calculations, estimates of average segregation tendency based on the zero-K energy spectrum deviate from experimental observations. To resolve this problem, thermodynamic integration (TI) methods based on molecular dynamics (MD) simulations are used to determine the per-site segregation free energies of Y at representative GB sites, which show contributions beyond harmonic approximations can be important for certain GB sites at high temperatures. A surrogate model of per-site segregation free energy is constructed from a small set of TI data points using stacking cross-validation regressors and physics-informed descriptors. This model is applied to predict the Y segregation free energy spectra for thousands of GB sites in Mg STGBs with uncertainty quantification. The average segregation tendency predicted by the spectral approach based on the free energy spectra agrees well (within the uncertainty range) with experimental observations for micro-scale polycrystalline Mg alloys at typical thermomechanical processing temperatures (500 ∼ 800 K), where thermodynamic equilibrium states are likely to be achieved due to fast diffusion.

Impact of Ionic Strength and Charge Density on Donnan Potential in the NaCl-Cation Exchange Membrane System

This work aims to theoretically investigate the effect of both the fixed charge density of ion exchange membranes and the ionic strength of the treated aqueous NaCl solution on the generated Donnan potential at thermodynamic equilibrium conditions. The direct objective of our work is to calculate the equilibrium concentration of the Cl− co-ion inside a swelled cation-exchange membrane equilibrated with a water/NaCl system. Two activity coefficient models are employed, i.e., the Debye–Huckel (DH) model (as a reference model) and the Meissner model, which is known for its applicability in treating concentrated solutions. Experimental data available in the literature for Donnan potential are used to verify model predictions. Our study confirms that a high fixed charge density is required to counterbalance the deterioration in membrane selectivity encountered in high-salinity systems. The DH model can be safely used to predict the Donnan potential for feed compositions up to 0.1 M. At higher compositions, the DH model significantly overestimates the predicted (absolute) Donnan potential compared to the Meissner model. The osmotic pressure resulting from the difference in ionic concentration between the membrane phase and the feed phase is found to have insignificant effects on the Donnan potential. The equilibrium computations and methodology are presented in a general way that enables handling multivalent electrolyte systems such as CaCl2.

Charged anisotropic compact stellar models under gravitational decoupling scheme

The aim of this paper is to obtain new physically admissible exact anisotropic stellar models via gravitational decoupling technique. This will be done by taking Korkina and Orlyanskii model solution as a seed solution and extend it to an anisotropic domain via gravitational decoupling through the minimal geometric deformation (MGD) approach. We analyze the physical properties of four compact star models Her [Formula: see text] (Mass [Formula: see text], [Formula: see text][Formula: see text]km), LMC [Formula: see text] ([Formula: see text], [Formula: see text][Formula: see text]km), PSR [Formula: see text] ([Formula: see text], [Formula: see text][Formula: see text]km) and PSR [Formula: see text] ([Formula: see text], [Formula: see text][Formula: see text]km). We demonstrate the stability conditions of the obtained solution by plotting energy conditions, velocity of sound, adiabatic index and all the thermodynamic parameters and equilibrium conditions via TOV equation, etc. We found that the results are physically well behaved and also fulfill the requirement of stability criteria inside the anisotropic fluid sphere. We study the physical features of the solutions in detail, analytically and graphically for the four compact stars Her [Formula: see text], LMC [Formula: see text], PSR [Formula: see text] and PSR [Formula: see text]. Based on the results we realized that the extended gravitational decoupling technique is very effective for the analysis of the interior of the compact stellar structures.

High temperature effects in hypersonic double-wedge flow simulations

Numerical simulations of inviscid hypersonic flow over a double-wedge geometry are conducted. High temperature effects are studied using a local thermodynamic equilibrium based model for air. A finite volume based flow solver is developed by combining a weighted essentially non-oscillatory scheme with an approximate Riemann solver. An iterative method to compute shock polars under local thermodynamic equilibrium conditions is suggested. Numerical simulations are conducted to study the effects of changes in geometry, upstream temperature, and upstream velocity. A range for the second wedge angle is identified for which the solution becomes oscillatory. An explanation for this oscillatory nature of the solution is suggested. Existence of a hysteresis phenomenon is also identified. A change in the nature of interaction is observed with changes in upstream temperature and upstream velocity. Local thermodynamic equilibrium based results are compared to those obtained using a calorically perfect gas model for air. Significant differences are observed. Effects of viscosity on the flow field are also studied.

NLTE Analysis of High-Resolution H-Band Spectra, V: Neutral Sodium

In order to derive sodium abundances and investigate the effects of non-local thermodynamic equilibrium (NLTE) on the formation of H-band Na I lines, we update the sodium atomic model by incorporating collision rates with hydrogen from new quantum-mechanical calculations. The differential Na abundances for 13 sample stars are obtained by analyzing high-resolution H-band spectra from the Apache Point Observatory Galactic Evolution Experiment (APOGEE) and optical spectra under both local thermodynamic equilibrium (LTE) and NLTE conditions. Consistent abundances from both bands suggest that our updated atomic model is valid for studying the formation of H-band Na I lines. Our calculations show that, in our stellar parameter space, NLTE effects are negative and can result in corrections larger than −0.4 dex on optical lines. The corrections on H-band Na I lines are typically small, within about 0.05 dex, but not negligible if accurate sodium abundance is desired. We note that the [Na/Fe] ratios favor the theoretical galactic chemical model.

The Distribution of High-excitation OCS Emission Around the Cep A-East Protostellar Cluster

The Cepheus A East high-mass star-forming region has been mapped at 1.4 mm using the OCS(17–16) and (18–17) lines observed with the IRAM 30 m antenna. Contour maps and high-resolution line profiles reveal the association of OCS with both (i) the hot-core region, and (ii) with the NE, SE, and S outflows driven by the young stellar objects. This confirms that OCS is among the main S-molecules observed in the gas-phase after thermal evaporation due to protostellar heating or shocks due to propagation of protostellar jets. Adopting Local Thermodynamic Equilibrium conditions, optically thin emission, and a temperature of 100 K, the total OCS column density (after correction for beam dilution) of the hot-core component is ∼1016 cm−2. For the outflow component, assuming a temperature range of 20–100 K, and extended emission, the OCS column density is ≤ 5 ×1014 cm−2 for a temperature ≥ 20 K.

Nonequilibrium kinetics effects in Richtmyer–Meshkov instability and reshock processes

Kinetic effects in the inertial confinement fusion ignition process are far from clear. In this work, we study the Richtmyer–Meshkov instability and reshock processes by using a two-fluid discrete Boltzmann method. The work begins by interpreting the experiment conducted by Collins and Jacobs (2002, J. Fluid Mech. 464, 113–136). It shows that the shock wave causes substances in close proximity to the substance interface to deviate more significantly from their thermodynamic equilibrium state. The thermodynamic non-equilibrium (TNE) quantities exhibit complex but inspiring kinetic effects in the shock process and behind the shock front. The kinetic effects are detected by two sets of TNE quantities. The first set includes , , , and , which correspond to the intensities of the non-organized momentum Flux (NOMF), Non-Organized Energy Flux (NOEF), the flux of NOMF and the flux of NOEF. All four TNE measures abruptly increase in the shock process. The second set of TNE quantities includes , and , which denote the entropy production rates due to NOMF, NOEF and their summation, respectively. The mixing zone is the primary contributor to , while the flow field region outside of the mixing zone is the primary contributor to . Additionally, each substance exhibits different behaviors in terms of entropy production rate, and the lighter fluid has a higher entropy production rate than the heavier fluid.

The CO(6−5) Protostellar Jet Driven by HH 212 as Imaged by ALMA-Band 9

During the earliest phases of the formation of a Sun-like star, jets play a key role in removing angular momentum from the accretion disk, allowing accretion onto the central star. Here we report, for the first time, the bipolar fast (∼150 km s−1) jet driven by the archetypical HH 212, as imaged on scales of ∼100 au by CO(6–5). Adopting Local Thermodynamic Equilibrium conditions, and optically thin emission, we derive the total CO column densities in the jet lobes: ∼1017 cm−2. Both jet lobes are 1200 au long. The observations have been performed using the ALMA Early Science operations, showing how the ALMA interferometer can be efficiently used in its Band 9 (>600 GHz) to investigate of protostellar jet.

Numerical simulation of frost heave of saturated soil considering thermo‐hydro‐mechanical coupling

AbstractFrost heave can lead to both the ground uplifting and frost heave pressure under different circumstances, and cause many engineering problems. To describe the characteristics of frost heave under various thermo‐hydro‐mechanical (THM) coupling conditions and calculate both the frost heave amount and the frost heave pressure, the coupled THM process, as well as the phase change of the pore water, should be considered for freezing soil. In this paper, thermodynamic equilibrium conditions in saturated freezing soil were derived to account for the mechanical effect on the cryogenic suction and unfrozen saturation of pore water during phase transition. Then the governing equations were developed considering the water flow, heat transfer, stress equilibrium, phase change, ice segregation, and their complex interactions. Based on that, a numerical model considering fully THM coupling is presented within the framework of finite element provided by COMSOL. Both frost heave amount tests and frost heave pressure tests were simulated to verify the proposed model. Then the model was applied to subgrades with different types of soil and different boundary conditions, to reveal the characteristics of frost heave amount and frost heave pressure under different conditions, and at the same time to demonstrate the model's applicative prospect.

Modeling the Chromosphere and Transition Region of Planet-hosting Star GJ 436

Abstract Ahead of upcoming space missions intending to conduct observations of low-mass stars in the ultraviolet (UV) spectral region it becomes imperative to simultaneously conduct atmospheric modeling from the UV to the visible (VIS) and near-infrared (NIR). Investigations on extended spectral regions will help to improve the overall understanding of the diversity of spectral lines arising from very different atmospheric temperature regions. Here we investigate atmosphere models with a chromosphere and transition region for the M2.5V star GJ 436, which hosts a close-in Hot Neptune. The atmosphere models are guided by observed spectral features from the UV to the VIS/NIR originating in the chromosphere and transition region of GJ 436. High-resolution observations from the Hubble Space Telescope and Calar Alto high-Resolution search for M dwarfs with Exo-earths with Near-infrared and optical Echelle Spectrographs (CARMENES) are used to obtain an appropriate model spectrum for the investigated M dwarf. We use a large set of atomic species considered in nonlocal thermodynamic equilibrium conditions within our PHOENIX model computations to approximate the physics within the low-density atmospheric regions. In order to obtain an overall match for the nonsimultaneous observations, it is necessary to apply a linear combination of two model spectra, where one of them better reproduces the UV lines while the other better represents the lines from the VIS/NIR range. This is needed to adequately handle different activity states across the observations.