Nonequilibrium Energy Research Articles

Nonequilibrium energy transport and nonclassical correlations of photons in a two-mode circuit quantum electrodynamic system

Nonequilibrium energy transport and nonclassical correlations of photons in a two-mode circuit quantum electrodynamic system

Thermodynamics of the Quantum Mpemba Effect.

We investigate the quantum Mpemba effect from the perspective of nonequilibrium quantum thermodynamics by studying relaxation dynamics of quantum systems coupled to a Markovian heat bath, which are described by Davies maps. Starting from a state with coherences in the energy eigenbasis, we demonstrate that an exponential speedup to equilibrium will always occur if the state is transformed to a diagonal state in the energy eigenbasis, provided that the spectral gap of the generator is defined by a complex eigenvalue. When the transformed state has a higher nonequilibrium free energy, we argue using thermodynamic reasoning that this is a genuine quantum Mpemba effect. Furthermore, we show how a unitary transformation on an initial state can always be constructed to yield the effect and demonstrate our findings by studying the dynamics of both the nonequilibrium free energy and the irreversible entropy production in single and multiqubit examples.

A theoretical framework for multi-physics modeling of poro-visco-hyperelasticity-induced time-dependent fracture of blood clots

Fracture resistance of blood clots plays a crucial role in physiological hemostasis and pathological thromboembolism. Although recent experimental and computational studies uncovered the poro-viscoelastic property of blood clots and its connection to the time-dependent deformation behavior, the effect of these physical processes on clot fracture and the underlying fracture mechanisms are not well understood. This work aims to formulate a thermodynamically consistent, multi-physics theoretical framework for describing the time-dependent deformation and fracture of blood clots. This theory concurrently couples fluid transport through porous fibrin networks, non-linear visco-hyperelastic deformation of the solid skeleton, solid-fluid interactions, mechanical degradation of tissues, gradient enhancement of energy, and protein unfolding of fibrin molecules. The constitutive relations of tissue constituents and the governing equation of fluid transport are derived within the framework of porous media theory by extending non-linear continuum thermodynamics at large strains. A physics-based, compressible network model is developed for the fibrin network of blood clots to describe its mechanical response. The kinetic equations of the internal variables, introduced for describing the non-linear viscoelastic deformation, non-local damage driving force and protein unfolding, are formulated according to the thermodynamics principles by incorporating a non-equilibrium energy of fibrin networks, a gradient-enhanced energy, and a stretch-induced energy of fibrin molecules, respectively, into the total free energy density function. An energy-based damage model is developed to predict the damage and fracture of blood clots, and an evolving regularization parameter is proposed to limit the damage zone bandwidth. The proposed model is implemented into finite element code by writing subroutines and is experimentally validated using single-edge cracked clot specimens with different constituents. The fracture of blood clots subject to different loading conditions is simulated, and the mechanisms of clot fracture are systematically analyzed. Computational results show that this model can accurately capture the experimentally measured deformation and fracture. The viscoelasticity and fluid transport play essential roles in the fracture of blood clots under physiological loading.

Nonequilibrium dissolution behaviors and mass-transfer parameters for a CO2/heavy-oil system

CO2 nonequilibrium dissolution in heavy oil was thoroughly studied, and the relevant mass-transfer parameters were determined. Experiments were conducted at different scales, including a single ultrathin microfluidic channel and ultrathin bulk-phase cell. A continuum-scale simulator coupled with an external real-time programing command was developed to determine the mass-transfer parameters, including the intraphase effective diffusion coefficients and interphase nonequilibrium mass-transfer rates. The former were correlated with the solvent concentration and chemical potential of the system, while the latter were calculated using nonequilibrium chemical potential decay, which was correlated with the system pressure and free energy. The newly developed simulator was verified using literature data from various experimental scales, including PVT cells and microfluidics. The simulator incorporates the effect of nonequilibrium free energy on interphase mass transfer in quiescent molecular diffusion-dominated processes, providing a viable technique for accurately simulating continuum-scale mass transfer, particularly in solvent-based injection.

Effect of multi-temperature models on heat transfer and electron behavior in hypersonic flows

In hypersonic computational fluid dynamics, the two-temperature (2-T) model is widely used to simulate thermochemical nonequilibrium. The 2-T model incorporates translational-rotational and electron-electronic-vibrational energies, assuming that the integrated energies have the equivalent temperature. In this study, multi-T models are constructed to accurately predict the effects on heat flux and free electrons due to the separation of energy modes under hypersonic environments. The three-temperature (3-T) model separates the electron-electronic energy from the electron-electronic-vibrational energy of the 2-T model. The 3-T model can accurately predict the distribution and temperature of free electrons by separating the energy of free electrons, which has different characteristics from heavy particles. The four-temperature model treats rotational energy as a nonequilibrium energy mode, distinct from translational-rotational energy. While the rotational temperature reaches equilibrium rapidly at low temperatures, at high-temperature regime rotational temperature shows a relaxation time similar to that of vibrational temperature, which cannot be ignored. To develop multi-T models, electron-vibrational relaxation and translational-rotational relaxation, which are omitted in the 2-T model, are considered. Various flight test and ground facility conditions are analyzed to verify the effects of electron and heat flux under circumstances that include shock, expansion, and shock wave boundary layer interaction. The results of the multi-T models show significant differences in electron temperature and distribution caused by electron-electronic nonequilibrium. Additionally, rotational nonequilibrium increases the shock standoff distance and alters the electron distribution at high altitudes. The heat flux difference across multi-T models is found to be negligible, except in the high degree of ionization condition.

Bidirectional path-based non-equilibrium simulations for binding free energy

Estimating free energy is a fundamental computational challenge, especially in complex biological systems characterised by numerous degrees of freedom. In this study, we investigate the potential of leveraging non-equilibrium free energy estimators within path-based approaches; this offers an appealing feature of inherent parallelism. Building upon our prior work on protein-ligand binding free energy calculations, we develop its non-equilibrium counterpart. We begin by validating our computational strategy on a simple toy model and then extend our analysis to the well-established trypsin-benzamidine complex, serving as a benchmark system. Subsequently, we apply this method to a more intricate, relevant pharmaceutical system to evaluate the performance of our computational pipeline on this complex system. Our results not only demonstrate the feasibility of this approach but also shed light on potential limitations. Furthermore, we showcase the capabilities of the Jarzynski and Crooks estimators employed in our study.

Designing Advanced Amorphous/Nanocrystalline Alloys by Controlling the Energy State.

Amorphous alloys, also known as metallic glasses, exhibit many advanced mechanical, physical, and chemical properties. Owing to the nonequilibrium nature, their energy states can vary over a wide range. However, the energy relaxation kinetics are very complex and composed of various types that are coupled with each other. This makes it challenging to control the energy state precisely and to study the energy-properties relationship. This brief review introduces the recent progresses on studying the enthalpy relaxation kinetics during isothermal annealing, for example, the observation of two-step relaxation phenomenon, the detection of relaxation unit (relaxun), the key role of large activation entropy in triggering memory effect, the influence of glass energy state on nanocrystallization. Based on the above knowledge, a new strategy is proposed to design a series of amorphous alloys and their composites consisting of nanocrystals and glass matrix with superior functional properties by precisely controlling the nonequilibrium energy states. As the typical examples, Fe-based amorphous alloys with both advanced soft magnetism and good plasticity, Gd-based amorphous/nanocrystalline composites with large magnetocaloric effect, and Fe-based amorphous alloys with high catalytic performance are specifically described.

Growth-induced stability in modified SLE curve

In this study, the non-equilibrium free energy corresponding to the curve generated by a modified stochastic Loewner evolution (SLE), which is driven by the Langevin equation, is theoretically investigated. Under certain conditions, we prove that the time derivative of the (generalized) free energy expressed by Kullback-Leibler divergence between the probability distributions of the curve and driving function has a positive value, indicating the negativity of Gibbs entropy production. In addition, it was implied that, in a certain restriction, the free energy can be expressed as a function of a Lyapunov-type exponent of the driving function. These results show a dissipative nature of conformal dynamics, and indicate the growth-induced stability of the modified SLE curve.

An improved continuum model for hypersonic thermal nonequilibrium flow in the near-continuum regime

In this work, the rarefied Couette flow of diatomic gases with thermal nonequilibrium effects is investigated by the direct simulation Monte Carlo (DSMC) method, and a macroscopic computational model is developed to consider the local rarefaction effects for diatomic gases in the near-continuum regime. The nonlinear transport properties of the diatomic gases are studied, indicating that effective viscosity and effective translational thermal conductivity in the shear nonequilibrium state are affected by translational nonequilibrium effects, which obey the same laws for both monatomic and diatomic gases. The transport coefficients of internal energy modes are affected by both translational nonequilibrium and internal energy relaxation, therefore, the effective rotational and vibrational thermal conductivities are related to the effective viscosity through a modified Eucken relation that accounts for internal energy relaxation. Conclusively, effective constitutive relations are newly established as a function of the shear nonequilibrium parameter and the modified Eucken factors for thermal nonequilibrium flows, and these are integrated into the macroscopic two-temperature model. Subsequently, it is assessed in the simulation of hypersonic flows over flat plates and cylinders at various Knudsen numbers. The results show that the surface shear stress and heat flux obtained by the proposed model agree well with the DSMC results, indicating significantly improved performance compared to the conventional Navier–Stokes two-temperature model for hypersonic flows in the near-continuum regime.

Bond Selective Photochemistry at Metal Nanoparticle Surfaces: CO Desorption from Pt and Pd.

The use of visible photon fluxes to influence catalytic reactions on metal nanoparticle surfaces has attracted attention based on observations of reaction mechanisms and selectivity not observed under equilibrium heating. These observations suggest that photon fluxes can selectively impact the rates of certain elementary steps, creating nonequilibrium energy distributions among various reaction pathways. However, quantitative studies validating these hypotheses on metal nanoparticle surfaces are lacking. We examine the influence of continuous wave visible photon fluxes on the CO desorption rates from 1 to 2 nm diameter Pt and Pd nanoparticle surfaces supported on γ-Al2O3. Temperature-programmed desorption measurements quantified via diffuse reflectance infrared Fourier transform spectroscopy demonstrate that visible photon fluxes significantly enhanced the rate of CO desorption from Pt nanoparticles in a wavelength-dependent manner. 440 nm photons most efficiently promoted CO desorption from Pt nanoparticle surfaces, aligning with the excitation energy for the interfacial electronic transition within the Pt-CO bond. Conversely, visible photon fluxes had no measurable influence on CO desorption rates from Pd nanoparticle surfaces after accounting for photon-induced heating. Density functional theory calculations demonstrate that the Pt-CO bond exhibits a narrower LUMO resonance, stronger coupling between the photoexcitation and forces induced on the metal-C bond, and vibrational energy dissipation that more effectively couples to desorption as compared to Pd-CO. These results demonstrate the specificity photons provide in facilitating chemical reactions on metal nanoparticle surfaces and substantiate the idea that photon fluxes can steer processes and outcomes of catalytic reactions in ways not achievable by equilibrium heating.

Raman time-delay in attosecond transient absorption of strong-field created krypton vacancy

Strong field ionization injects a transient vacancy in the atom which is entangled to the outgoing photoelectron. When the electron is finally detached, the ion is populated at different excited states with part of coherence information lost. The preserved coherence of matter after interacting with intense short pulses has important consequences on the subsequent nonequilibrium evolution and energy relaxation. Here we employ attosecond transient absorption spectroscopy to measure the time-delay of resonant transitions of krypton vacancy during their creation. We have observed that the absorptions by the two spin-orbit split states are modulated at different paces when varying the time-delay between the near-infrared pumping pulse and the attosecond probing pulse. It is shown that the coupling of the ions with the remaining field leads to a suppression of ionic coherence. Comparison between theory and experiments uncovers that coherent Raman coupling induces time-delay between the resonant absorptions, which provides insight into laser-ion interactions enriching attosecond chronoscopy.

Ab initio theory of the nonequilibrium adsorption energy

While first-principles calculations of electrode-molecule adsorption play an indispensable role in obtaining atomic-level understanding in surface science and electrochemistry, a significant challenge remains because the adsorption energy is well-defined only in equilibrium. Herein, a theory to calculate the electric enthalpy for electrified interfaces is formulated within the multi-space constrained-search density functional theory (MS-DFT), which provides the nonequilibrium total energy of a nanoscale electrode-channel-electrode junction. An additional MS-DFT calculation for the electrode-only counterpart that maintains the same bias voltage allows one to identify the internal energy of the channel as well as the electric field and the channel polarization, which together determine the electric enthalpy and the nonequilibrium adsorption energy. Application of the developed scheme to the water-Au and water-graphene interface models shows that the Au and graphene electrodes induce very different behaviors in terms of the electrode potential-dependent stabilization of water configurations. The theory developed here will be a valuable tool in the ongoing effort to obtain atomic-scale understanding of bias-dependent molecular reorganizations in electrified interfaces.

Meteorological Data and Spectral Analyses of Non-Equilibrium Processes in Water during the Total Solar Eclipse of 11.08.1999 in Bulgaria

There are partial or total solar eclipses every year on our planet. They are observed from relatively small areas. From 1950 to 2100, three total solar eclipses fell within the territory of Bulgaria. The two solar eclipses from the 20th century were observed on 15.02.1961 and 11.08.1999. The next total solar eclipse will happen on 3.09.2081. The partial solar eclipses in Bulgaria were on 3.10.2005, 29.03.2006, 1.09.2008, 4.01.2011, and 25.10.2022. The question of the influence of solar eclipses on the Earth’s atmosphere, water, and living organisms is an area of interest for many researchers. In this connection, studies have been conducted on atmospheric and water parameters during partial and total solar eclipses. Most investigations were performed with meteorological data – temperature and humidity. In the last 30 years, other methods have also been applied for the investigations of solar eclipses – spectral methods with infrared (IR) spectroscopy, studies of magnetic and electric fields, polarization, and measurements of the parameters of the fluids in plants. Our studies have used meteorological methods and analyses. For the effects on the water, spectral methods are applied to the non-equilibrium energy spectrum (NES) and differential non-equilibrium spectrum (DNES). A deionized water sample examined during the solar eclipse on 11.08.1999 was used, aiming to analyze the parameters of NES and DNES. The deionized water control sample was tested on 10.08.1999 at the same time as the solar eclipse of the next day. The results of our research show relatively rapid and significant changes in air parameters during a solar eclipse, which are most prominent immediately after its culmination. The conditions of non-equilibrium arising during the solar eclipse allow for studying the restructuring of the hydrogen bonds of water molecules. The results of the current studies prove that the solar eclipse’s significantly affect water which is the primary substance in the Nature and living organisms. These data are consistent with other ones which also prove that, during a solar eclipse, the structure of water undergoes significant changes. By influencing the water, this natural phenomenon affects the whole Nature and all living organisms on the planet.

Emergent energy dissipation in quantum limit

Energy dissipation is of fundamental interest and crucial importance in quantum systems. However, whether energy dissipation can emerge without backscattering inside topological systems remains a question. As a hallmark, we propose a microscopic picture that illustrates energy dissipation in the quantum Hall (QH) plateau regime of graphene. Despite the quantization of Hall, longitudinal, and two-probe resistances (dubbed as the quantum limit), we find that the energy dissipation emerges in the form of Joule heat. It is demonstrated that the non-equilibrium energy distribution of carriers plays much more essential roles than the resistance on energy dissipation. Eventually, we suggest probing the phenomenon by measuring local temperature increases in experiments and reconsidering the dissipation typically ignored in realistic topological circuits.

4D microvelocimetry reveals multiphase flow field perturbations in porous media

Many environmental and industrial processes depend on how fluids displace each other in porous materials. However, the flow dynamics that govern this process are still poorly understood, hampered by the lack of methods to measure flows in optically opaque, microscopic geometries. We introduce a 4D microvelocimetry method based on high-resolution X-ray computed tomography with fast imaging rates (up to 4 Hz). We use this to measure flow fields during unsteady-state drainage, injecting a viscous fluid into rock and filter samples. This provides experimental insight into the nonequilibrium energy dynamics of this process. We show that fluid displacements convert surface energy into kinetic energy. The latter corresponds to velocity perturbations in the pore-scale flow field behind the invading fluid front, reaching local velocities more than 40 times faster than the constant pump rate. The characteristic length scale of these perturbations exceeds the characteristic pore size by more than an order of magnitude. These flow field observations suggest that nonlocal dynamic effects may be long-ranged even at low capillary numbers, impacting the local viscous-capillary force balance and the representative elementary volume. Furthermore, the velocity perturbations can enhance unsaturated dispersive mixing and colloid transport and yet, are not accounted for in current models. Overall, this work shows that 4D X-ray velocimetry opens the way to solve long-standing fundamental questions regarding flow and transport in porous materials, underlying models of, e.g., groundwater pollution remediation and subsurface storage of CO2 and hydrogen.

Optimization of nonequilibrium free energy harvesting illustrated on bacteriorhodopsin

Harvesting free energy from the environment is essential for the operation of many biological and artificial systems. We use techniques from stochastic thermodynamics to investigate the maximum rate of harvesting achievable by optimizing a set of reactions in a Markovian system, possibly under various kinds of topological, kinetic, and thermodynamic constraints. This question is relevant for the optimal design of new harvesting devices as well as for quantifying the efficiency of existing systems. We first demonstrate that the maximum harvesting rate can be expressed as a constrained convex optimization problem. We illustrate it on bacteriorhodopsin, a light-driven proton pump from Archaea, which we find is close to optimal under realistic conditions. In our second result, we solve the optimization problem in closed-form in three physically meaningful limiting regimes. These closed-form solutions are illustrated on two idealized models of unicyclic harvesting systems. Published by the American Physical Society 2024

Thermodynamic Insights into Symmetry Breaking: Exploring Energy Dissipation across Diverse Scales.

Symmetry breaking is a phenomenon that is observed in various contexts, from the early universe to complex organisms, and it is considered a key puzzle in understanding the emergence of life. The importance of this phenomenon is underscored by the prevalence of enantiomeric amino acids and proteins.The presence of enantiomeric amino acids and proteins highlights its critical role. However, the origin of symmetry breaking has yet to be comprehensively explained, particularly from an energetic standpoint. This article explores a novel approach by considering energy dissipation, specifically lost free energy, as a crucial factor in elucidating symmetry breaking. By conducting a comprehensive thermodynamic analysis applicable across scales, ranging from elementary particles to aggregated structures such as crystals, we present experimental evidence establishing a direct link between nonequilibrium free energy and energy dissipation during the formation of the structures. Results emphasize the pivotal role of energy dissipation, not only as an outcome but as the trigger for symmetry breaking. This insight suggests that understanding the origins of complex systems, from cells to living beings and the universe itself, requires a lens focused on nonequilibrium processes.

Catalysis in action via elementary thermal operations

We investigate catalysis in the framework of elementary thermal operations (ETOs), leveraging the distinct features of such operations to illuminate catalytic dynamics. As groundwork, we establish new technical tools that enhance the computability of state transition rules for ETOs. Specifically, we provide a complete characterisation of state transitions for a qutrit system and special classes of initial states of arbitrary dimension. By employing these tools in conjunction with numerical methods, we find that by adopting a small catalyst, including just a qubit catalyst, one can significantly enlarge the set of state transitions for a qutrit system. This advancement notably narrows the gap of reachable states between ETOs and generic thermal operations. Furthermore, we decompose catalytic transitions into time-resolved evolution, which critically enables the tracking of nonequilibrium free energy exchanges between the system and bath. Our results provide evidence for the existence of simple and practicable catalytic advantage in thermodynamics while offering insight into analysing the mechanism of catalytic processes.

Real-time observation of non-equilibrium phonon-electron energy and angular momentum flow in laser-heated nickel.

Identifying the microscopic nature of non-equilibrium energy transfer mechanisms among electronic, spin, and lattice degrees of freedom is central to understanding ultrafast phenomena such as manipulating magnetism on the femtosecond timescale. Here, we use time- and angle-resolved photoemission spectroscopy to go beyond the often-used ensemble-averaged view of non-equilibrium dynamics in terms of quasiparticle temperature evolutions. We show for ferromagnetic Ni that the non-equilibrium electron and spin dynamics display pronounced variations with electron momentum, whereas the magnetic exchange interaction remains isotropic. This highlights the influence of lattice-mediated scattering processes and opens a pathway toward unraveling the still elusive microscopic mechanism of spin-lattice angular momentum transfer.

Quantum non-Markovianity, quantum coherence and extractable work in a general quantum process.

A key concept in quantum thermodynamics is extractable work, which specifies the maximum amount of work that can be extracted from a quantum system. Different quantities are used to measure extractable work, the most prevalent of which are ergotropy and the difference between the non-equilibrium and equilibrium quantum free energies. Using the latter, we investigate the evolution of extractable work when an open quantum system undergoes a general quantum process described by a completely-positive and trace-preserving dynamical map. We derive a fundamental equation of thermodynamics for such processes as a relation between the distinct sorts of energy change in such a way that the first and the second law of thermodynamics are combined. We then identify the contributions from the reversible and irreversible processes in this equation and demonstrate that they are respectively responsible for the evolution of heat and extractable work of the open quantum system. Furthermore, we show how this correspondence between irreversibility and extractable work has the potential to provide a clear explanation of how the quantum properties of a system affect its extractable work evolution. Specifically, we establish this by directly connecting the change in extractable work with the change in standard quantifiers of quantum non-Markovianity and quantum coherence during a general quantum process. We illustrate these results with two examples.