Non-equilibrium Conditions Research Articles

Research on Non-Equilibrium Dynamics Theory in Chemical Thermodynamics

Non-equilibrium dynamics theory is an important branch of chemical thermodynamics, widely applied in describing complex chemical reaction systems far from equilibrium. With the advancement of modern science and technology, an increasing number of chemical reactions exhibit unique behaviors under non-equilibrium conditions, such as self-organization and periodic oscillations—nonlinear phenomena. This paper systematically explores the distinctions between non-equilibrium and equilibrium states, introduces the fundamental principles of non-equilibrium thermodynamics, and analyzes cutting-edge issues such as nonlinear phenomena and multi-scale dynamics. Additionally, it discusses the specific applications of non-equilibrium dynamics in far-from-equilibrium reactions, heterogeneous catalysis, and industrial chemical processes, addressing both theoretical and experimental challenges. Through the combination of theoretical analysis and practical application, this paper aims to provide new insights and methodologies for research on non-equilibrium dynamics in the field of chemistry.

Modeling Water Clusters: Spectral Analyses, Gaussian Distribution, and Linear Function during Time

Our experimental and theoretical studies have consistently revealed the presence of water clusters in various environments, particularly under hydrophobic conditions, where slower hydrogen ion interactions prevail. Crucial methods like Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FTIR) method have played a pivotal role in our understanding of these clusters, unveiling their potential medical applications. The stability and behavior of these clusters can be influenced by factors such as metal ions’ presence, leading to stable clusters’ formation. This potential for medical applications should inspire hope and further research. Moreover, our research has revealed that water clusters exhibit characteristics of dissipative structures, demonstrating the self-organization under physical, chemical, or thermal changes akin to Rayleigh–Benard convection cells. This dynamic and significant behavior supports the notion that water’s role transcends simple chemistry, potentially influencing biological processes at a fundamental level. The interaction of water clusters with their environment and the ability to maintain non-equilibrium states through the energy exchanges further underscores their complexity and significance in both natural and technological contexts. Water filtration is a process for improving water quality. The effect is re-structuring hydrogen bonds and structuring water clusters, most of which are hexagonal. In our research, we applied filtered water using patented EVOdrop Swiss technology.

Ultrafast spectroscopy of coherent phonons across the pressure driven insulator to metal phase transition in V2O3

Nowadays, materials science is moving towards the understanding and control of materials in nonequilibrium states by making use of perturbative techniques to investigate their dynamical responses. From this perspective, the use of ultrashort light pulses seems to be a relevant approach as it can selectively address different degrees of freedom in solid-state systems and more particularly electrons. Such a method can help to decipher the physical phenomena arising from electronic correlations and complements a more conventional methodology where the phase diagrams of materials are investigated at thermodynamical equilibrium. Here, we combine femtosecond optical spectroscopy and a high-pressure setup to monitor the ultrafast out-of-equilibrium photo response of a V2O3 thin film across the pressure driven insulator-to-metal transition. The experimental results demonstrate the possibility to use the spectroscopy of coherent phonons as a thermodynamical phase marker in V2O3 thin films. In addition, the frequency behavior of the ultrafast coherent phonon mode (A1g character) seems to reflect the manifestation of a strong coupling between the lattice and electronic degrees of freedom near first-order transition lines with a pronounced drop in frequency around the critical pressure. Published by the American Physical Society 2024

Minimum-dissipation principle for synchronized stochastic oscillators far from equilibrium

We prove a linear stability-dissipation relation (SDR) for q-state Potts models driven far from equilibrium by a nonconservative force. At a critical coupling strength, these models exhibit a synchronization transition from a decoherent into a synchronized state. In the vicinity of this transition, the SDR connects the entropy production rate per oscillator to the phase-space contraction rate, a measure of stability, in a simple way. For large but finite systems, we argue that the SDR implies a minimum-dissipation principle for driven Potts models as the dynamics selects stable nonequilibrium states with least dissipation. This principle holds arbitrarily far from equilibrium, for any stochastic dynamics, and for all q. Published by the American Physical Society 2024

Strongly Enhanced Electronic Bandstructure Renormalization by Light in Nanoscale Strained Regions of Monolayer MoS2/Au(111) Heterostructures.

Understanding and controlling the photoexcited quasiparticle (QP) dynamics in monolayer (ML) transition metal dichalcogenides (TMDs) lays the foundation for exploring the strongly interacting, nonequilibrium two-dimensional (2D) QP and polaritonic states in these quantum materials and for harnessing the properties emerging from these states for optoelectronic applications. In this study, scanning tunneling microscopy/spectroscopy (STM/scanning tunneling spectroscopy) with light illumination at the tunneling junction is performed to investigate the QP dynamics in ML MoS2 on an Au(111) substrate with nanoscale corrugations. The corrugations on the surface of the substrate induce nanoscale local strain in the overlaying ML MoS2 single crystal, which result in energetically favorable spatial regions where photoexcited QPs, including excitons, trions, and electron-hole plasmas, accumulate. These strained regions exhibit pronounced electronic bandstructure renormalization as a function of the photoexcitation wavelength and intensity as well as the strain gradient, implying strong interplay among nanoscale structures, strain, and photoexcited QPs. In conjunction with the experimental work, we construct a theoretical framework that integrates nonuniform nanoscale strain into the electronic bandstructure of a ML MoS2 lattice using a tight-binding approach combined with first-principle calculations. This methodology enables better understanding of the experimental observation of photoexcited QP localization in the nanoscale strain-modulated electronic bandstructure landscape. Our findings illustrate the feasibility of utilizing nanoscale architectures and optical excitations to manipulate the local electronic bandstructure of ML TMDs and to enhance the many-body interactions of excitons, which is promising for the development of nanoscale energy-adjustable optoelectronic and photonic technologies, including quantum emitters and solid-state quantum simulators for interacting exciton polaritons based on engineered periodic nanoscale trapping potentials.

Non-equilibrium thermodynamics in NMR: understanding quadrupolar spin-1 systems.

In this study, we explore the non-equilibrium thermodynamics of a quantum system,
specifically focusing on spin-1 quadrupole nuclei. By employing fundamental principles
from quantum mechanics and statistical mechanics, we aim to understand the behavior
of the quadrupole spin-1 nuclei when subjected to external perturbations. Our analysis
involves the investigation of the system's dynamic response to non-equilibrium conditions through the manipulation of a work parameter. By treating work as a random
variable, we gather data from multiple cycles of finite duration, enabling us to compute
the complete distribution of the work generated during this process. Through these
finite-time non-equilibrium process data, we are able to determine equilibrium values
for important quantities such as the difference in free energy between the initial and
final states of the system. Additionally, we explore various properties of the system's
work distribution.

Active RNA synthesis patterns nuclear condensates.

Biomolecular condensates are membraneless compartments that organize biochemical processes in cells. In contrast to well-understood mechanisms describing how condensates form and dissolve, the principles underlying condensate patterning - including their size, number and spacing in the cell - remain largely unknown. We hypothesized that RNA, a key regulator of condensate formation and dissolution, influences condensate patterning. Using nucleolar fibrillar centers (FCs) as a model condensate, we found that inhibiting ribosomal RNA synthesis significantly alters the patterning of FCs. Physical theory and experimental observations support a model whereby active RNA synthesis generates a non-equilibrium state that arrests condensate coarsening and thus contributes to condensate patterning. Altering FC condensate patterning by expression of the FC component TCOF1 impairs ribosomal RNA processing, linking condensate patterning to biological function. These results reveal how non-equilibrium states driven by active chemical processes regulate condensate patterning, which is important for cellular biochemistry and function.

Observation of reversible conformational interconversion accompanied by 3p internal conversions in Rydberg-excited N,N-dimethylethylamine

Conformational dynamics has been well observed in the 3s Rydberg state of amines, whereas its observation in higher-energy, non-equilibrium 3p Rydberg states is very rare, especially for a reversible conformational transition that could compete with other non-adiabatic transitions. Herein, we report the observation of a reversible conformational interconversion phenomenon in the 3p Rydberg excited-state dynamics of N,N-dimethylethylamine (DMEA). Upon electronic excitation, a forward and backward interconversion between the initially prepared 3p_l and 3p_h conformers accompanied by 3p internal conversions occurs, resulting in a 3p_l/3p_h equilibrium ratio of 61 %/39 % within ∼1.5 ps. The ensuing parallel internal conversions from the 3p_l to 3s_l and 3p_h to 3s_h deposit about 1.80 eV of vibrational energy into the 3s state, enabling a fast conformational interconversion between the 3s_h and 3s_l conformers to proceed within ∼2.0 ps. The final 3s_l/3s_h equilibrium ratio was determined to be 76 %/24 %. This work presents a real-time observation of the entire conformational interconversion process initiating from the higher-energy 3p states and finally reaching an equilibrium on the lower-energy 3s state.

Influence of boundary effect on supersonic flows and non-equilibrium condensation in a Laval nozzle for natural gas dehydration

The natural gas extraction process is often accompanied by large amounts of water vapor, so natural gas dehydration is the first step in achieving natural gas utilization. Current work focuses on a clean technology that captures water vapor in natural gas through expansion refrigeration. Using water vapor as a medium, a mathematical model for predicting spontaneous condensation caused by non-equilibrium state is established and validated. The influence of boundary effect including surface roughness and wall temperature on supersonic flows and non-equilibrium condensation are studied. The surface roughness affects the energy and momentum exchange between the fluid in the main stream area and near the wall, and thus affects the Wilson point, boundary layer, and non-equilibrium condensation. When the roughness rises by 0.1 mm, the boundary layer thickness increases by 56.7%, and the radial nucleation range decreases by 11.4% from y=±5.27 mm to y=±4.67 mm. The influence of wall temperature on the central area in the nozzle is not significant, but it affects the presence of liquid phase. The radial scope of liquid-phase drops by 3.58% when the wall temperature increases by 100 K.

Energy Aware Technology Mapping of Genetic Logic Circuits.

Energy and its dissipation are fundamental to all living systems, including cells. Insufficient abundance of energy carriers─as caused by the additional burden of artificial genetic circuits─shifts a cell's priority to survival, also impairing the functionality of the genetic circuit. Moreover, recent works have shown the importance of energy expenditure in information transmission. Despite living organisms being non-equilibrium systems, non-equilibrium models capable of accounting for energy dissipation and non-equilibrium response curves are not yet employed in genetic design automation (GDA) software. To this end, we introduce Energy Aware Technology Mapping, the automated design of genetic logic circuits with respect to energy efficiency and functionality. The basis for this is an energy aware non-equilibrium steady state model of gene expression, capturing characteristics like energy dissipation─which we link to the entropy production rate─and transcriptional bursting, relevant to eukaryotes as well as prokaryotes. Our evaluation shows that a genetic logic circuit's functional performance and energy efficiency are disjoint optimization goals. For our benchmark, energy efficiency improves by 37.2% on average when comparing to functionally optimized variants. We discover a linear increase in energy expenditure and overall protein expression with the circuit size, where Energy Aware Technology Mapping allows for designing genetic logic circuits with the energetic costs of circuits that are one to two gates smaller. Structural variants improve this further, while results show the Pareto dominance among structures of a single Boolean function. By incorporating energy demand into the design, Energy Aware Technology Mapping enables energy efficiency by design. This extends current GDA tools and complements approaches coping with burden in vivo.

Tuning Transduction from Hidden Observables to Optimize Information Harvesting.

Biological and living organisms sense and process information from their surroundings, typically having access only to a subset of external observables for a limited amount of time. In this Letter, we uncover how biological systems can exploit these accessible degrees of freedom to transduce information from the inaccessible ones with a limited energy budget. We find that optimal transduction strategies may boost information harvesting over the ideal case in which all degrees of freedom are known, even when only finite-time trajectories are observed, at the price of higher dissipation. We apply our results to red blood cells, inferring the implemented transduction strategy from membrane flickering data and shedding light on the connection between mechanical stress and transduction efficiency. Our framework offers novel insights into the adaptive strategies of biological systems under nonequilibrium conditions.

A review of the preparation and prospects of amorphous alloys by mechanical alloying

The preparation of amorphous alloys typically involves rapid solidification from a molten state. Since 1980, when Yermo and Koch first achieved the amorphization of alloys by mechanical alloying (MA), researchers worldwide have developed a strong interest in this technique, which allows for the amorphization of alloy components in a non-equilibrium state at room temperature without the need for a liquid phase. MA has been widely applied in the fabrication of both equilibrium and non-equilibrium materials over the past few decades, and it remains a crucial technique for the production of amorphous alloys. This review selectively summarizes research on MA-produced amorphous alloys reported over the past two decades. It explores key issues of MA amorphization from the perspectives of both the mechanism of amorphization and the design of amorphous compositions through MA. The first section primarily elucidates commonly used methods for designing amorphous compositions at present, while the second section expounds on the transformation mechanism of MA amorphization. The third section summarizes the influence of alloy element additions on its properties, and the fourth section mainly illustrates the contribution of computational advancements to the exploration of amorphous mechanisms and the design of amorphous compositions. Finally, prospects for the development trend of preparing amorphous alloys through MA are discussed.

Dissipative Self-Assembly of Patchy Particles under Nonequilibrium Drive: A Computational Study.

Inspired by biology and implemented using nanotechnology, the self-assembly of patchy particles has emerged as a pivotal mechanism for constructing complex structures that mimic natural systems with diverse functionalities. Here, we explore the dissipative self-assembly of patchy particles under nonequilibrium conditions, with the aim of overcoming the constraints imposed by equilibrium assembly. Utilizing extensive Monte Carlo (MC) and Molecular Dynamics (MD) simulations, we provide insight into the effects of external forces that mirror natural and chemical processes on the assembly rates and the stability of the resulting assemblies comprising 8, 10, and 13 patchy particles. Implemented by a favorable bond-promoting drive in MC or a pulsed square wave potential in MD, our simulations reveal the role these external drives play in accelerating assembly kinetics and enhancing structural stability, evidenced by a decrease in the time to first assembly and an increase in the duration the system remains in an assembled state. Through the analysis of an order parameter, entropy production, bond dynamics, and interparticle forces, we unravel the underlying mechanisms driving these advancements. We also validated our key findings by simulating a larger system of 100 patchy particles. Our comprehensive results not only shed light on the impact of external stimuli on self-assembly processes but also open a promising pathway for expanding the application by leveraging patchy particles for novel nanostructures.

Mixed equilibrium/nonequilibrium effects govern surface mobility in polymer glasses

Using angle-resolved X-ray photoelectron spectroscopy, sum-frequency generation vibrational spectroscopy, contact angle measurements, and molecular dynamics simulations, we verify that the glass transition temperature (Tg) of polymer glass is lower near the free surface. However, the experimental Tg-gradients showed a linear variation with depth (z) from the free surface, while the simulated equilibrium Tg-gradients exhibited a double exponential z-dependence. In typical simulations, Tg is determined based on the relaxation time of the system reaching a prescribed threshold value at equilibrium. Conversely, the experiments determined Tg by observing the unfreezing of molecular mobility during heating from a kinetically arrested, nonequilibrium glassy state. To investigate the impact of nonequilibrium effects on the Tg-gradient, we reduced the thermal annealing time in simulations, allowing the system to fall out of equilibrium. We observe a decrease in the relaxation time and the emergence of a modified z-dependence consistent with a linear Tg-gradient near the free surface. We further validate the impact of nonequilibrium effects by studying the dependence of the Tg on the heating/cooling rate for polymer films of varying thickness (h). Our experimental results reveal significant variations in the Tg-heating/cooling rate dependence with h below the bulk Tg, which are also observed in simulation when the simulated system is not equilibrated. We explain our findings by the reduction in mass density within the inner region of the system under nonequilibrium conditions, as observed in simulation, and recent research indicating a decrease in the local Tg of a polymer when placed next to a softer material.

Ultrafast Yttrium Hydride Chemistry at High Pressures via Non-equilibrium States Induced by an X-ray Free Electron Laser.

Controlling the formation and stoichiometric content of the desired phases of materials has become of central interest for a variety of fields. The possibility of accessing metastable states by initiating reactions by X-ray-triggered mechanisms over ultrashort time scales has been enabled by the development of X-ray free electron lasers (XFELs). Utilizing the exceptionally high-brilliance X-ray pulses from the EuXFEL, we report the synthesis of a previously unobserved yttrium hydride under high pressure, along with nonstoichiometric changes in hydrogen content as probed at a repetition rate of 4.5 MHz using time-resolved X-ray diffraction. Exploiting non-equilibrium pathways, we synthesize and characterize a hydride in a Weaire-Phelan structure type at pressures as low as 125 GPa, predicted using a crystal structure search, with a hydrogen content of 4.0-5.75 hydrogens per cation, that is enthalpically metastable on the convex hull.

Soluble Model of a Nonequilibrium Steady State: The Van Kampen Objection and Other Lessons.

A simple model of charge transport is provided by a classical particle in a random potential and a dissipative coupling to the environment. The corresponding nonequilibrium steady state (NESS) can be determined analytically when both the disorder and dissipation are weak. We use it to illuminate some foundational issues in nonequilibrium statistical mechanics. We show that at nonlinear level dissipative response sensitively depends on the system-environment coupling, and the range of validity of the linear response theory is set by this coupling. This validates the Van Kampen objection. We also show that the principle of minimum entropy production does not determine the NESS beyond linear order in the electric field, while entropy maximization fails to produce the correct NESS already at linear order.

Stability analysis of a vertical cantilever pipe with lumped masses conveying two-phase flow

This study investigates the vibration behavior of a vertical cantilever pipe conveying gas-liquid two-phase flow, focusing on the influence of lumped masses attached to the vertical cantilevered pipe. The governing motion equation based on small deflection Euler–Bernoulli beam theory is solved by using the generalized integral transforms technique. The proposed solution approach was first validated against available numerical and experimental results in the literature. The effects of the mass ratios, number and position of lumped masses on the stability of the pipe are investigated. Numerical results show that the parameters of the lumped masses affect significantly the stability of the pipe conveying two-phase flow, by altering the fluid–structure interaction dynamics and impacting natural frequencies and vibration modes of the pipe. Specifically, as the position of a single lumped mass moves downward from the fixed end to the free end, the critical flow velocity initially increases and subsequently decreases, thereby reducing the stability of pipe. Moreover, increasing the number of lumped masses significantly impacts the critical flow velocity due to the mass ratios and locations. Notably, modal “jumping” phenomena are observed, which demonstrate continuous shifts between equilibrium and non-equilibrium states in the cantilever pipes. These findings are crucial for ensuring the safe operation of pipes with discrete masses across various engineering applications.

Harmonic chain driven by active Rubin bath: transport properties and steady-state correlations

Characterizing the properties of an extended system driven by active reservoirs is a question of increasing importance. Here, we address this question in two steps. We start by investigating the dynamics of a probe particle connected to an ‘active Rubin bath’: a linear chain of overdamped run-and-tumble particles. We derive exact analytical expressions for the effective noise and dissipation kernels, acting on the probe and show that the active nature of the bath leads to a modified fluctuation–dissipation relation. In the next step, we study the properties of an activity-driven system, modelled by a chain of harmonic oscillators connected to two such active reservoirs at the two ends. We show that the system reaches a non-equilibrium stationary state (NESS), remarkably different from that generated due to a thermal gradient. We characterize this NESS by computing the kinetic temperature profile, spatial and temporal velocity correlations of the oscillators, and the average energy current flowing through the system. It turns out that the activity drive leads to the emergence of two characteristic length-scales, proportional to the activities of the reservoirs. Strong signatures of activity are also manifest in the anomalous short-time decay of the velocity autocorrelations. Finally, we find that the energy current shows a non-monotonic dependence on the activity drive and reversal in direction, corroborating previous findings.

Estimation of gas diffusion coefficient for gas/oil-saturated porous media systems by use of early-time pressure-decay data: An experimental/numerical approach

This paper presented a novel numerical method for estimating the gas diffusion coefficient based on the early-time pressure-decay data. Experimentally, “flooding–soaking” procedures were developed to perform the gas diffusion in an oil-saturated tight core under different gas phase volume conditions. After flooding, the capillary bundle model was used to calculate the oil–gas contact area. The early-time pressure-decay data of the gas phase were monitored and recorded during the soaking process. Theoretically, a non-equilibrium inner boundary condition coupled with the characteristics of experimental early-time pressure had been incorporated to develop a diffusion model for a gas/oil-saturated tight core system. Based on gas-phase mass balance equations and gas equation of state, the diffusion coefficients were optimized once the discrepancy between experimental data and numerical solutions was minimized. According to the estimated results in this study, the CH4 diffusion coefficients were 3.74 × 10−11 and 3.86 × 10−11 m2/s in tight core saturated with crude oil, respectively. Moreover, the oil–gas contact area significantly impacts the diffusion flux in oil-saturated porous media. Specifically, an additional 10% contact area results in a 75% increase in CH4 diffusion mass. In addition, with the application of our proposed model to CH4/bitumen and CO2/bitumen systems, the diffusion coefficients were in close agreement with the results reported in previous literature, indicating that the proposed model was applicable to both gas/liquid and gas/liquid-saturated porous media systems.

Theoretical Analysis of Self-Shrinkage Spheroidization of Irregular Degradable Polymer Powder under Thermodynamic Nonequilibrium State

Laser three-dimensional (3D) printing offers significant advantages in integrating the shape and function of regenerative tissues through biomimetic manufacturing. However, its effectiveness is limited by the lack of specialized biopolymer powders—while solvent methods that use residual solvents produce powders with poor biocompatibility, mechanical methods result in irregularly shaped crystals. In this study, a biopolymer powder spheroidization and shaping technology, which utilizes the evolution of irregular powders into spheres with minimal surface free energy in the molten state, is proposed based on the thermodynamic principle of minimum energy. Initially, the motion trajectory and temperature field of the poly(L-lactic acid) (PLLA) powder during spheroidization were quantitatively assessed and optimized using Stokes’ law and Fourier's principle. Subsequently, the cohesive forces and aggregation kinetics of the polymer chains were calculated using molecular dynamics. Finally, based on these calculations, a phase-field model was constructed to simulate the evolution of the spheroidization rate and deduce the optimal parameters for the process. This precise approach enhances PLLA spheroidization control for laser 3D printing, improves part densification and surface quality, and offers a clean and efficient path for preparing high-quality PLLA spheroidized powder for laser 3D printing.