Non-equilibrium Kinetics Research Articles

A nonequilibrium kinetic model of high-resolution vibrational energy transfer in RDX from selective IR excitation.

In this paper, we develop a model based on a second quantization-with anharmonic phonon scattering and the phonon Boltzmann transport equation-to study precise high-resolution nonequilibrium vibrational energy transfer (VET) under selective phonon excitation in cyclotrimethylene trinitramine. We simulate mid-infrared pump-probe spectroscopy and observe a prompt appearance (<1ps) of broad-spectrum intensity, which agrees well with experimental data in the literature. The selective excitation of phonons at different frequencies reveals distinct VET pathways and the kinetic evolution of mode occupations as the system reaches a new equilibrium temperature. Three types of transition mechanisms are found to play outsized roles in terms of the amount of energy transferred and the transfer rate: (1) vibrational modes close to the excited frequencies typically respond faster and reach higher temperatures regardless of the excitation frequency; (2) the overtone pathway connecting the modes near 550 and 1150cm-1 is an important bridge between far- and mid-IR; and (3) fast aggregation of energy at 2800cm-1 mediates transfer to/from high frequencies through a second overtone pathway involving modes near 1400cm-1. In addition, by monitoring the temperature of the N-N/N-O stretching modes, strong coupling between those modes and the C-H stretching modes is found. The coupling likely draws the vibrational modes close to both the proton transfer transition state for HONO elimination and the N-N stretching for bond cleavage. The high-resolution understanding of the nonequilibrium kinetics of phonons provides important insight into the energy transfer and initiation mechanisms of molecular solids due to external stimuli.

Complexity of confined water vitrification and its glass transition temperature

The ability of vitrification when crossing the glass transition temperature (Tg) of confined and bulk water is crucial for myriad phenomena in diverse fields, ranging from the cryopreservation of organs and food to the development of cryoenzymatic reactions, frost damage to buildings, and atmospheric water. However, determining water's Tg remains a major challenge. Here, we elucidate the glass transition of water by analyzing the calorimetric behavior of nano-confined water across various pore topologies (diameters: 0.3 to 2.5 nm). Our approach involves subjecting confined water to annealing protocols to identify the temperature and time evolution of nonequilibrium glass kinetics. Furthermore, we complement this calorimetric approach with the dynamics of confined water, as seen by broadband dielectric spectroscopy and linear calorimetric measurements, including the fast scanning technique. This study demonstrated that confined water undergoes a glass transition in the temperature range of 170 to 200 K, depending on the confinement size and the interaction with the confinement walls. Moreover, we also show that the thermal event observed at ~136 K must be interpreted as an annealing prepeak, also referred to as the "shadow glass transition." Calorimetric measurements also allow the detection of a specific heat step above 200 K, which is insensitive to annealing and, thereby, interpreted as a true thermodynamic transition. Finally, by connecting our results to bulk water behavior, we offer a comprehensive understanding of confined water vitrification with potential implications for numerous applications.

Nonequilibrium fast-lithiation of Li4Ti5O12 thin film anode for LIBs

Li4Ti5O12 (LTO) is known for its zero-strain characteristic in electrochemical applications, making it a suitable material for fast-charging applications. Here, we systematically studied the quasi-equilibrium and non-equilibrium lithium-ion transportation kinetics in LTO thin-film electrodes, across a range of scales from the crystal lattice to the microstructured electrodes. At the crystal lattice scale, during the non-equilibrium lithiation process, lithium ions are dispersedly embedded into the 16c position, resulting in more 8a → 16c migration compared with the quasi-equilibrium lithiation, and forming numerous fast lithium diffusion channels inside the LTO lattice. At the microstructural electrode scale, optical spectrum characterizations supported the “nano-filaments” lithiation model in polycrystalline LTO thin-film electrodes during the lithiation process. Our results reveal the patterns of lithium migration and distribution within the LTO thin film electrode under the non-equilibrium and quasi-equilibrium lithiation process, offering profound insights into the potential optimization strategies for enhancing the performance of fast-charging thin film batteries.

Characterization of water propellant in an electron cyclotron resonance thruster

A coaxial electron cyclotron resonance thruster operating on water vapor propellant is investigated to determine the influence of molecular propellant chemistry on thruster performance. The performance is characterized at different mass flow rates (0.1–0.4 mg/s) and powers (20–200 W) using a thrust stand, ion energy analyzer, and spectrometer. Experimental data are compared to the results from a theoretical model that includes non-equilibrium chemical kinetics. The thruster is observed to transition from a state where power deposition favors propellant dissociation and ionization into a state where it favors electron heating and ion acceleration. The results suggest that the majority of plasma heating occurs in a core region that surrounds the thruster antenna and that propellant flow outside this region is not efficiently utilized for propulsion.

Single-Step Control of Liquid-Liquid Crystalline Phase Separation by Depletion Gradients.

Fine-tuning nucleation and growth of colloidal liquid crystalline (LC) droplets, also known as tactoids, is highly desirable in both fundamental science and technological applications. However, the tactoid structure results from the trade-off between thermodynamics and nonequilibrium kinetics effects, and controlling liquid-liquid crystalline phase separation (LLCPS) in these systems is still a work in progress. Here, a single-step strategy is introduced to obtain a rich palette of morphologies for tactoids formed via nucleation and growth within an initially isotropic phase exposed to a gradient of depletants. The simultaneous appearance is shown of rich LC structures along the depleting potential gradient, where the position of each LC structure is correlated with the magnitude of the depleting potential. Changing the size (nanoparticles) or the nature (polymers) of the depleting agent provides additional, precise control over the resulting LC structures through a size-selective mechanism, where the depletant may be found both within and outside the LC droplets. The use of depletion gradients from depletants of varying sizes and nature offers a powerful toolbox for manipulation, templating, imaging, and understanding heterogeneous colloidal LC structures.

Inverted nucleation for photoinduced nonequilibrium melting.

Ultrafast photoinduced melting provides an essential platform for studying nonequilibrium phase transitions by linking the kinetics of electron dynamics to ionic motions. Knowledge of dynamic balance in their energetics is essential to understanding how the ionic reaction is influenced by femtosecond photoexcited electrons with notable time lag depending on reaction mechanisms. Here, by directly imaging fluctuating density distributions and evaluating the ionic pressure and Gibbs free energy from two-temperature molecular dynamics that verified experimental results, we uncovered that transient ionic pressure, triggered by photoexcited electrons, controls the overall melting kinetics. In particular, ultrafast nonequilibrium melting can be described by the reverse nucleation process with voids as nucleation seeds. The strongly driven solid-to-liquid transition of metallic gold is successfully explained by void nucleation facilitated by photoexcited electron-initiated ionic pressure, establishing a solid knowledge base for understanding ultrafast nonequilibrium kinetics.

From Milliseconds to Minutes: Melittin Self-Assembly from Concerted Non-Equilibrium Pressure-Jump and Equilibrium Relaxation Nuclear Magnetic Resonance.

Non-equilibrium kinetics techniques like pressure-jump nuclear magnetic resonance (NMR) are powerful in tracking changes in oligomeric populations and are not limited by relaxation rates for the time scales of exchange that can be probed. However, these techniques are less sensitive to minor, transient populations than are Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion experiments. We integrated non-equilibrium pressure-jump and equilibrium CPMG relaxation dispersion data to fully map the kinetic landscape of melittin tetramerization. While monomeric peptides weakly form dimers (Kd,D/M ≈ 26 mM) whose population never exceeds 1.6% at 288 K, dimers associate tightly to form stable tetrameric species (Kd,T/D ≈ 740 nM). Exchange between the monomer and dimer, along with exchange between the dimer and tetramer, occurs on the millisecond time scale. The NMR approach developed herein can be readily applied to studying the folding and misfolding of a wide range of oligomeric assemblies.

Ion-selective response of visible light photoswitchable indole-hemithioindigo: toward chemical sensing of fluoride and hydroxide.

The chemical sensing of hydrophilic anions such as F- and OH- is of significant importance but also presents considerable challenges. Herein, the thermal E to Z isomerization of a visible-light-responsive photoswitch (HTI-In) is utilized to address this challenge for the first time. The isomerization of HTI-In is dependent on the concentration of F- and OH-, and exhibits excellent selectivity toward F- and OH- over other common anions and cations. Unlike irreversible chemodosimeters and other conventional fluorescent probes, the photodynamic sensing of F- and OH- (demonstrated in solvents and polyurethane hydrogels) is based on a non-equilibrium chemical kinetics and can be operated fully reversibly.

Phase separation of a magnetic fluid: Asymptotic states and nonequilibrium kinetics.

We study self-assembly in a colloidal suspension of magnetic particles by performing comprehensive molecular dynamics simulations of the Stockmayer (SM) model, which comprises spherical particles decorated by a magnetic moment. The SM potential incorporates dipole-dipole interactions along with the usual Lennard-Jones interaction and exhibits a gas-liquid phase coexistence observed experimentally in magnetic fluids. When this system is quenched from the high-temperature homogeneous phase to the coexistence region, the nonequilibrium evolution to the condensed phase proceeds with the development of spatial as well as magnetic order. We observe density-dependent coarsening mechanisms-a diffusive growth law ℓ(t)∼t^{1/3} in the nucleation regime and hydrodynamics-driven inertial growth law ℓ(t)∼t^{2/3} in the spinodal regimes. [ℓ(t) is the average size of the condensate at time t after the quench.] While the spatial growth is governed by the expected conserved order parameter dynamics, the growth of magnetic order in the spinodal regime exhibits unexpected nonconserved dynamics. The asymptotic morphologies have density-dependent shapes which typically include the isotropic sphere and spherical bubble morphologies in the nucleation region, and the anisotropic cylinder, planar slab, cylindrical bubble morphologies in the spinodal region. The structures are robust and nonvolatile, and exhibit characteristic magnetic properties. For example, the oppositely magnetized hemispheres in the spherical morphology impart the characteristics of a Janus particle to it. The observed structures have versatile applications in catalysis, drug delivery systems, memory devices, and magnetic photonic crystals, to name a few.

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.

Non-Equilibrium behavior of dissociated hydrogen in historic Nuclear thermal propulsion reactors

Hydrogen gas dissociation in Nuclear Thermal Propulsion (NTP) analyses and models is often assumed universally at chemical equilibrium or neglected entirely. This study examines the non-equilibrium chemical kinetics of high-speed dissociating hydrogen within a range of reactor temperature profiles using historic NTP engine inlet and outlet conditions. Below 1600 K, all reactors should be modeled at equilibrium unless somehow disrupted off the equilibrium concentration where it must be modeled in non-equilibrium. Above 1600 K, NTP systems should assume non-equilibrium behavior to accurately represent high-speed flow. However, analysis of historic NTP reactors all achieved equilibrium, modeled at the highest possible flow speeds, at the reactor outlet. Historic atomic hydrogen molar fractions at the outlet were less than 0.5%. These findings and analyses provide useful and validated assumptions for all NTP reactors for dissociation aiding future CFD analysis.

Two-dimensional calculation model for hazardous substances formation in combustion products of a spark-ignition engine

Introduction (problem statement and relevance). Improvement of environmental parameters of internal combustion engines is one of the most relevant tasks of the domestic transport engineering. Calculation support allows reducing the time and raising the efficiency of works for refining of the bench work process in order to meet the required parameters. The paper is devoted to development of a two-dimensional calculation model for hazardous substances formation in combustion products of spark-ignition engines based on the non-equilibrium kinetic models of formation of nitrogen oxides and carbon monoxide.Methodology and research methods. Computational methods for differential equations (ordinary and partial ones) are applied. Non-equilibrium kinetics of hazardous substances formation in combustion products is considered. The work process is calculated based on a combination of the mesh control-volume method and determination of the observable flame rate based on the experimental data (taking into account the development stage of the flame source).Scientific novelty and results. The new calculation method for flame propagation in the spark-ignition engine is suggested. The developed model combines such advantages as good predictability and short time of calculation.Practical significance. The model can be applied, in particular, to preliminary planning of three-dimensional calculations of the work process or their check in the absence of experimental data (at the stage of preliminary/concept design). The calculation results can be used as initial data for modeling of the exhaust gas aftertreatment (additional purification) system.

A simple semiempirical model for the static polarizability of ions

Abstract A concise analytical model for the static dipole polarizability of ionized atoms and molecules is created for the first time. As input, it requires, alongside the polarizability of neutral counterpart of a given ion, only the charge and elemental composition. This physically motivated semiempirical model is based on a number of established regularities in polarizability of charged monatomic and polyatomic compounds. In order to adjust it, the results of quantum chemistry calculations and gas-phase measurements available for a broad range of ionized multielectron species are employed. To counteract the appreciable bias in the literature data toward polarizability of monoatomic ions, for some molecular ions of general concern the results of the authors’ own density functional theory calculations are additionally invoked. A total of 541 data points are used to optimize the model. It is demonstrated that the model we suggested has reasonable (given the substantial uncertainties of the reference data) accuracy in predicting the static isotropic polarizability of arbitrarily charged ions of any size and atomic composition. The resulting polarizability estimates are found to achieve a coefficient of determination of 0.93 for the assembled data set. The created analytic tool is universally applicable and might be advantageous for some applications, where there is an urgent need for rapid low-cost evaluation of the static gas-phase polarizability of ionized atoms and molecules. This is especially relevant to constructing the complex models of nonequilibrium chemical kinetics aimed at precise describing the observable refractive index (dielectric permittivity) of plasma flows. The data sets that support the findings of this study are openly available in Science Data Bank at https://...

Low temperature state-to-state vibrational kinetics of O + N2(v) and N + O2(v) collisions

Starting from an equilibrium initial condition at 3000 K, the non-equilibrium vibrational kinetics of a 500 K atmospheric pressure N2/N/O2/O/NO mixture is investigated with a zero-dimensional time-dependent numerical solver. Attention is devoted to the O + N2(v) and N + O2(v) collisions, thanks to new QCT state-to-state rates from the literature. The Zeldovich and the dissociation–recombination reactions are considered; for the N + O2(v) collisions the inelastic vT processes are considered too. Interpolation formulae of the corresponding rates are proposed.The mixture behaviour depends on the combined effects of the different processes, however under the conditions adopted the forward second Zeldovich reaction switches on the kinetics towards a new equilibrium.The aim of the present study is to open the door to more complex applications of plasmas in the fields of the plasma medicine, the fertilizers production and, more in general, of the nitrogen fixation.

Two-step devitrification of ultrastable glasses

The discovery of ultrastable glasses raises novel challenges about glassy systems. Recent experiments studied the macroscopic devitrification of ultrastable glasses into liquids upon heating but lacked microscopic resolution. We use molecular dynamics simulations to analyze the kinetics of this transformation. In the most stable systems, devitrification occurs after a very large time, but the liquid emerges in two steps. At short times, we observe the rare nucleation and slow growth of isolated droplets containing a liquid maintained under pressure by the rigidity of the surrounding glass. At large times, pressure is released after the droplets coalesce into large domains, which accelerates devitrification. This two-step process produces pronounced deviations from the classical Avrami kinetics and explains the emergence of a giant lengthscale characterizing the devitrification of bulk ultrastable glasses. Our study elucidates the nonequilibrium kinetics of glasses following a large temperature jump, which differs from both equilibrium relaxation and aging dynamics, and will guide future experimental studies.

Scientific school of non-equilibrium aeromechanics in Saint Petersburg State University

The review is devoted to the foundation and development of the scientific school of S. V. Vallander at the Leningrad (now St Petersburg) State University. The achievements of the scientific school in the development of the kinetic theory methods for modeling nonequilibrium flows, construction of rigorous self-consistent mathematical models of varying complexity for strong and weak deviations from equilibrium, and the use of the developed models in challenging problems of modern aerodynamics are discussed. Particular attention is paid to the study of non-equilibrium kinetics and transport processes in carbon dioxide, identification of key relaxation mechanisms of polyatomic molecules, derivation of physically based reduced hybrid models, and optimization of non-equilibrium flow numerical simulations using modern machine learning methods. Correct description of electronic excitation in the kinetics and transport processes, models of local equilibrium gas flows with multiple ionization, and features of modeling bulk viscosity in polyatomic gases are discussed.

Studying the Intermolecular Interactions, Structural Dynamics, and Non-Equilibrium Kinetics of Cilnidipine Infiltrated into Alumina and Silica Pores.

In the present study, the behavior of the calcium channel blocker cilnidipine (CLN) infiltrated into silica (SiO2) and anodic aluminum oxide (AAO) porous membranes characterized by a similar pore size (d = 8 nm and d = 10 nm, respectively) as well as the bulk sample has been investigated using differential scanning calorimetry, broadband dielectric spectroscopy (BDS), and Fourier-transform infrared spectroscopy (FTIR) techniques. The obtained data suggested the existence of two sets of CLN molecules in both confined systems (core and interfacial). They also revealed the lack of substantial differences in inter- and intramolecular dynamics of nanospatially restricted samples independently of the applied porous membranes. Moreover, the annealing experiments (isothermal time-dependent measurements) performed on the confined CLN clearly indicated that the whole equilibration process under confinement is governed by structural relaxation. It was also found that the βanneal parameters obtained from BDS and FTIR data upon equilibration of both confined samples are comparable (within 10%) to each other, while the equilibration constants are significantly different. This finding strongly emphasizes that there is a close connection between the inter- and intramolecular dynamics under nanospatial restriction.

New Insights from Nonequilibrium Kinetics Studies on Highly Polar S-Methoxy-PC Infiltrated into Pores.

Herein, the annealing of highly polar (S)-(-)-4-methoxymethyl-1,3-dioxolan-2-one (S-methoxy-PC) within alumina and silica porous membranes characterized by different pore diameters was studied by means of dielectric spectroscopy. We found a significant slowing down of the structural dynamics of confined S-methoxy-PC with annealing time below and, surprisingly, also above the glass transition temperatures of the interfacial layer, Tg,interfacial. Furthermore, unexpectedly, a change in the slope of temperature dependencies of the characteristic time scale of this process τanneal, at Tg,interfacial for all confined samples, was reported. By modeling τanneal(T), we noted that the observed enormous variation of τanneal results from a decrease of the pore radius due to the vitrification of the interfacial molecules. This indicates that the enhanced dynamics of confined materials upon cooling is mainly controlled by the interfacial molecules.

Coupling plasma physics and chemistry in the PIC model of electric propulsion: Application to an air-breathing, low-power Hall thruster

This work represents a first attempt to include the complex variety of electron-molecule processes in a full kinetic particle-in-cell/test particle Monte Carlo model for the plasma and neutral gas phase in a Hall thruster. Particular emphasis has been placed on Earth’s atmosphere species for the air-breathing concept. The coupling between the plasma and the gas phase is self-consistently captured by assuming the cold gas approximation and considering gas-wall and gas recycling from the walls due to ion neutralization. The results showed that, with air molecular propellants, all the most relevant thruster performance figures degraded relative to the nominal case using Xe propellant. The main reasons can be ascribed to a reduced ionization cross-section, a larger gas ionization mean free path due to lighter mass air species, and additional electron collisional power losses. While vibrational excitations power losses are negligible, dissociation and electronic excitations compete with the ionization channel. In addition, for molecular oxygen, the large dissociation leads to even faster atoms, further reducing their transit time inside the discharge channel. Future studies are needed to investigate the role of non-equilibrium vibrational kinetics and metastable states for stepwise ionization.

Non-equilibrium plasma kinetics of CO2 in glow discharges: a comparison with existing modeling and experimental results

We report results obtained by our 0D, time-dependent self-consistent model for the description of the CO2 plasma kinetics in glow discharge conditions, comparing our results with the simulation and experimental results reported by Grofulovic et al (2018 Plasma Sources Sci. Technol. 27 115009; 2019 PhD Thesis) and Klarenaar et al (2017 Plasma Sources Sci. Technol. 26 115008). Our model is based on the simultaneous solution of the kinetic equations describing the vibrational, the electronic excited states and the plasma chemistry and of the electron Boltzmann equation for the calculation of the electron energy distribution function (eedf). The results for the vibrational level densities of CO2 show a satisfactory agreement with the Grofulovic’s model results, despite the differences in the vibrational energy level scheme and in the kinetic processes included with the correspondent rate coefficients, with a good match also with the corresponding experimental results. Moreover, conditions characterized by higher power density (5–50 W cm−3) have been investigated to understand the behavior of the CO2 plasma discharge when a higher vibrational excitation is present. Large deviations of the vibrational distributions of CO2 and CO from equilibrium ones are predicted both in discharge and post discharge conditions. In particular, the CO2 vibrational distribution presents a behavior similar to a Treanor distribution for v < 15 while a deactivation of the plateau in the vibrational distribution function after v > 15 appears as a consequence of the dissociation induced by vibrational excitation mechanism, i.e. pure vibrational mechanism, becoming important at higher power densities. Finally, the results dependence on the selection of the CO2 electron molecule dissociation cross section, i.e. Phelps (1973 J. Appl. Phys. 44 4464 or Cosby (1993 Report No. AD-A266 464 WL-TR-93-2004 (Dayton, OH: Wright-Patterson Airforce Base)), has been investigated, showing that its more opportune choice is still a problem to be discussed for the description of conditions in which the electron impact dissociation dominates the kinetics, while once vibrational excitation is activated, CO2 dissociation is essentially driven by vibrational-induced dissociation, depending to a minor extent from that choice.