Non-equilibrium Transformation Research Articles

Dynamic Active Sites In Situ Formed in Metal Nanoparticle Reshaping under Reaction Conditions.

Understanding the nonequilibrium transformation of nanocatalysts under reaction conditions is important because metastable atomic structures may be created during the process, which offers unique activities in reactions. Although reshaping of metal nanoparticles (NPs) under reaction conditions has been widely recognized, the dynamic reshaping process has been less studied at the atomic scale. Here, we develop an atomistic kinetic Monte Carlo model to simulate the complete reshaping process of Pt nanoparticles in a CO environment and reveal the in situ formation of atomic clusters on the NP surface, a new type of active site beyond conventional understanding, boosting the reactivities in the CO oxidation reaction. Interestingly, highly active peninsula and inactive island clusters both form on the (111) facets and interchange in varying states of dynamic equilibrium, which influences the catalytic activities significantly. This study provides new fundamental knowledge of nanocatalysis and new guidance for the rational design of nanocatalysts.

Role of interactions in nonequilibrium transformations.

For arbitrary nonequilibrium transformations in complex systems, we show that the distance between the current state and a target state can be decomposed into two terms: one corresponding to an independent estimate of the distance, and another corresponding to interactions, quantified using the relative mutual information between the variables. This decomposition is a special case of a more general decomposition involving successive orders of correlation or interactions among the degrees of freedom of the system. To illustrate its practical significance, we study the thermal relaxation of two interacting, optically trapped colloidal particles, where increasing pairwise interaction strength is shown to prolong the longevity of the time-dependent nonequilibrium state. Additionally, we study a system with both pairwise and triplet interactions, where our approach identifies their distinct contributions to the transformation. In more general setups where it is possible to control the strength of different orders of interactions, our findings provide a way to disentangle their effects and identify interactions that facilitate the transformation.

Melting and solidification dynamics during laser melting of reaction-based metal matrix composites uncovered by in-situ synchrotron X-ray diffraction

Laser additive manufacturing (AM) of reaction-based metal matrix composites (MMCs) involves highly complex and non-equilibrium material transformation behavior, including melting, dissolution, precipitation, and solidification. Yet, the dynamics and interplay of these phase transformation processes remain poorly understood, posing substantial challenges in identifying the microstructure formation mechanism, and predicting and controlling the microstructure in the printed parts. Here we performed the in-situ X-ray diffraction experiment to characterize the phase evolution dynamics of the 316L + 10 vol.%TiC system during laser melting, which provides direct and quantitative insights of the complex phase reaction and evolution dynamics under rapid heating and cooling conditions relevant to additive manufacturing of reaction-based MMCs. Further in-depth thermodynamic and kinetic calculations revealed that most of the phase evolution behavior observed in the in-situ X-ray diffraction experiment cannot be solely explained by widely used equilibrium thermodynamic models, and diffusion-controlled nonequilibrium dissolution and precipitation kinetics must be considered to elucidate the complex phase evolution behavior, including incomplete TiC dissolution, and three-step TiC precipitation. The three distinct types of precipitates generate unique hierarchical TiC micro- and nanostructures, which enhances the yield strength from 513 MPa to 877 MPa by 71 %, tensile strength from 628 MPa to 1054 MPa by 68 %, and Young's modulus from 193 GPa to 221 GPa by 14 %. The findings of our research provide the knowledge foundation for the design of unique microstructures and advanced MMC materials through laser AM.

Addressing Suboptimal Poses in Nonequilibrium Alchemical Calculations.

Alchemical transformations can be used to quantitatively estimate absolute binding free energies at a reasonable computational cost. However, most of the approaches currently in use require knowledge of the correct (crystallographic) pose. In this paper, we present a combined Hamiltonian replica exchange nonequilibrium alchemical method that allows us to reliably calculate absolute binding free energies, even when starting from suboptimal initial binding poses. Performing a preliminary Hamiltonian replica exchange enhances the sampling of slow degrees of freedom of the ligand and the target, allowing the system to populate the correct binding pose when starting from an approximate docking pose. We apply the method on 6 ligands of the first bromodomain of the BRD4 bromodomain-containing protein. For each ligand, we start nonequilibrium alchemical transformations from both the crystallographic pose and the top-scoring docked pose that are often significantly different. We show that the method produces statistically equivalent binding free energies, making it a useful tool for computational drug discovery pipelines.

Differential scanning calorimetry of aluminium EN AB-42000 alloy rheocasting semi-solid in different stage heating rates

Differential scanning calorimetry (DSC) is used to identify the thermal histories of samples to analyse and diagnose production and quality concerns connected to industrial rheocasting semi-solid alloy, that had undergone different tempers of aluminium alloy EN AB-42000 alloy. In this study, the solidus temperatures of several alloy samples are investigated using thermodynamic calculations and DSC observations in this work. The balance of important characteristics, including pseudo-eutectic, thermal sensitivity, heat flow, and enthalpies behaviour, of Al alloys has been investigated using experimental data from DSC and solid fractions. In addition, the choice of heating rates is critical as high rates can blur the two peaks in the mushy zone, while low rates lead to slower measurements. Using smaller sample weights and slower rates is preferable to obtain more accurate results. Analysing the shape of the fs curve, exact composition, and a reference composition without contaminants is essential for understanding complex behaviours, including pseudo-eutectic phenomena. The thermal sensitivity of compositions also plays a crucial role in the analysis. Despite heat flow decreasing with decreased sample weight, the measurement limit can still be exceeded at high heating or cooling rates (20 °C/min) during the eutectic reaction. The eutectic reaction exhibits higher peaks with enthalpies ranging from 360 to 430 mJ/g. However, drawing conclusions regarding trends in heating versus cooling or comparing low-mass and higher-mass samples can be challenging. The non-equilibrium transformation of the eutectic occurs within a more confined temperature range. Increasing rates lead to overlapping reactions, resulting in complex thermal behaviour.

Effect of static electric fields on liquid water, its structure, dynamics, and hydrogen bond asymmetry: A molecular dynamics simulation study of TIP4P/2005 water model.

We study the effect of static electric fields of 0.1, 0.4, and 1.0 V/nm on the hydrogen bond structure and dynamics of TIP4P/2005 water at 1bar and at temperatures between 300 and 200K using molecular dynamics simulations. At all these temperatures, simulating liquid water with electric fields of 0.1 and 0.4 V/nm has no additional effect on its structural and dynamical changes, which otherwise already take place due to cooling. However, the introduction of 1.0 V/nm field enhances the slowing down of liquid water dynamics, crystallizes it to cubic ice at 240 and 220K, and amorphizes it at 200K. At 240 and 220K, crystallization occurs within 5 and 50ns, respectively. An electric field of 1 V/nm increases the relaxation times in addition to what cooling does. We note that when liquid water's metastability limit is reached, crystallization is averted and amorphization takes place. Both equilibrium (liquid-solid) and non-equilibrium (liquid-amorphous) transformations are observed at 1 V/nm. Moreover, with an increase in the electric field, H-bonds become stronger. However, the donor-acceptor asymmetry (the difference between the strengths of two donor/acceptor bonds) remains even when crystallization or amorphization takes place. At low temperatures, increasing electric fields on liquid water increases both its crystallization and amorphization tendencies.

On the phase transformation pathway during localized grain boundary oxidation in an Fe-10 at% Cr alloy at 200ºC

We have performed short-term, controlled oxidation experiments of sputter deposited Fe-10 at% Cr alloy films at 200ºC. Nanoscale structural characterization by four-dimensional scanning transmission electron microscopy (4d-STEM) and chemical characterization by atom probe tomography (APT) have provided insights on the phase transformation pathway followed during localized, inward-progressing oxidation of grain boundaries at this low temperature. Direct nucleation of a metastable spinel-structured oxide, with suppression of the corundum-structured Cr2O3 has been observed even at the early stages. A ‘partitioning-free oxide nucleation mechanism’ under conditions of extremely restricted kinetics is proposed to explain the non-equilibrium transformation pathway.

Local structure transformations promoting high lithium diffusion in defect perovskite type structures

Defect perovskites, AxBO3 such as (Li3xLa2/3-x)TiO3, are attracting attention as high capacity electrodes in lithium-ion batteries. However, the mechanism enabling high lithium storage capacities has not been fully investigated. In this work, the reversible insertion and removal of lithium up to an average A-site cavity occupancy of 1.71 in the defect perovskite (Li0.18Sr0.66)(Ti0.5Nb0.5)O3 is investigated. It was shown that subtle lithium reorganization during lithiation has a significant impact on enabling high capacity. Contrary to previous studies, lithium was coordinated to triangular faces of Ti/Nb oxygen octahedra and offset from O4 windows between A-site cavities in the as-synthesised material. Upon electrochemical lithiation Li-Li repulsion redistributes of all the lithium towards the O4 window position resulting in a loss of lithium mobility. Surprisingly, the mobility is regained during over-lithiation and following multiple electrochemical cycles. It is suggested that lithium reorganisation into the center of the O4 window alleviates the Li-Li repulsion and modifies the diffusion behavior from site percolation to bond percolation. The results obtained provide valuable insight into the chemical drivers enabling higher capacities and enhanced diffusion in defect perovskites. More broadly the study delivers fundamental understanding on the non-equilibrium structural transformations occurring within electrode materials during repeated electrochemical cycles.

Continuous thermomajorization and a complete set of laws for Markovian thermal processes

The standard dynamical approach to quantum thermodynamics is based on Markovian master equations describing the thermalization of a system weakly coupled to a large environment, and on tools such as entropy production relations. Here we develop a new framework overcoming the limitations that the current dynamical and information theory approaches encounter when applied to this setting. More precisely, we introduce the notion of continuous thermomajorization, and employ it to obtain necessary and sufficient conditions for the existence of a Markovian thermal process transforming between given initial and final energy distributions of the system. These lead to a complete set of generalized entropy production inequalities including the standard one as a special case. Importantly, these conditions can be reduced to a finitely verifiable set of constraints governing non-equilibrium transformations under master equations. What is more, the framework is also constructive, i.e., it returns explicit protocols realizing any allowed transformation. These protocols use as building blocks elementary thermalizations, which we prove to be universal controls. Finally, we also present an algorithm constructing the full set of energy distributions achievable from a given initial state via Markovian thermal processes and provide a $\texttt{Mathematica}$ implementation solving $d=6$ on a laptop computer in minutes.

Stochastic normalizing flows as non-equilibrium transformations

Normalizing flows are a class of deep generative models that provide a promising route to sample lattice field theories more efficiently than conventional Monte Carlo simulations. In this work we show that the theoretical framework of stochastic normalizing flows, in which neural-network layers are combined with Monte Carlo updates, is the same that underlies out-of-equilibrium simulations based on Jarzynski’s equality, which have been recently deployed to compute free-energy differences in lattice gauge theories. We lay out a strategy to optimize the efficiency of this extended class of generative models and present examples of applications.

Active transformations of topological structures in light-driven nematic disclination networks

SignificanceTopological defects are marvels of nature. Understanding their structures is important for their applications in, for example, directed self-assembly, sensing, and photonic devices. There is recent interest in active motion and transformation of topological defects in active nematics. In these nonequilibrium systems, however, the motion and transformation of disclinations are difficult to control, thereby hindering their applications. Here, we propose a surface-patterned system engendering periodic three-dimensional disclinations, which can be excited by light irradiation and undergo a programmable transformation between different topological states. Continuum simulations recapitulating these topological structures characterize the bending, breaking, and relinking events of the disclinations during the nonequilibrium process. Our work provides an alternative dynamic system in which active transformation of topological defects can be engineered.

Decompression dynamics of high density amorphous ice above and below the liquid-liquid critical point

We investigate via numerical simulations of the TIP4P/Ice model the isothermal decompression of high density amorphous ice (HDA) mirroring the experimental protocol followed by recent experiments [H. K. Kim, et al., Science 370 , 978, 2020]. Taking advantage of the recent determination of the TIP4P/Ice liquid-liquid critical point, we decompress our samples at temperatures both below and above the critical temperature. We follow the crossover between high and low density, complementing the time evolution of the structure factor with the time evolution of microscopic descriptors. Our results support the interpretation of the experimental pathway as a structural change from high to low density states through a first-order transition line. In the simulation study we do not observe nucleation events, but rather a spinodal-like non-equilibrium transformation, which offers an explanation on why the decompression process even at sub-critical temperatures may result in a continuous time evolution of the density and of the microscopic descriptors.

Self-evolving materials based on metastable-to-stable crystal transition of a polymorphic polyolefin.

Living organisms can self-evolve with time in order to adapt to the natural environment. Analogically, self-evolving materials also show similar properties based on non-equilibrium structural transformation. The common design of these materials tends to rely on solutions and hydrogels, yet only little attention has been paid to dry materials. To break this limitation, a new principle for developing self-evolving materials from a commercialized polymorphic polyolefin via programmable crystal transition is proposed. The self-evolving materials can encode information on patterns and morphing by the metastable crystal phase. Dynamically, this phase transforms to the stable crystal phase so that the encoded information self-evolves with time, displaying the autonomous characteristic. Moreover, this process can be interrupted at an arbitrary time through solvent-induced recrystallization. These advantages have been demonstrated by fabricating an edible period indicator and imitating sophisticated human body language. It is believed that this work may inspire future research studies on self-evolving materials based on the non-equilibrium process of dry materials.

Structure Frustration Enables Thermal History-Dependent Responsive Behavior in Self-Healing Hydrogels

Biological soft tissues usually execute their functions via nonequilibrium and dynamic structural transformations. By contrast, functional hydrogels are mainly constructed by implementing static and equilibrium structures in the polymer network. Here, using polyampholyte hydrogel as a model system, we demonstrated that the nonequilibrium structure transformation in self-healing hydrogels enables the gels with many new features, including thermal history dependence, quick and asymmetric thermal response (instant transparent-to-turbid transition but slow turbid-to-transparent transition), tunable cloud point, tunable recovery time, and tiny changes in sample size and mechanical performance. These features make them distinct to conventional thermoresponsive hydrogels based on thermodynamic equilibrium and endow them with a new type of promising thermoresponsive materials. We revealed the structure change and studied the role of the thermal protocol on this thermoresponsive behavior by combining ultraviolet spectrum, small-angle X-ray scattering, rheology, and mechanical measurements. We also presented two conceptual applications of this thermoresponsive hydrogel in thermal imaging and security paper. We believe that this work will inspire future research on creating functional hydrogels via nonequilibrium structure transformations.

Gender and the future of macroeconomics: an evolutionary approach

Gender lends itself well to an evolutionary analysis which focuses on non-equilibrium change and transformation for individuals within society. Decomposition by such an important category as gender helps us understand the economy at the macro level, and design macroeconomic policy, better. It also provides the foundation for advocating equal gender rights and outcomes. But, where gendered policy issues arise in mainstream macroeconomics (income maldistribution, labour market composition, etc.), the subject matter is narrowed by its microfoundations, by focusing on GDP growth and on suboptimal outcomes being explained by market imperfections. An approach which takes gender seriously requires the different epistemology which arises from feminism: it does not rely on dualistic categorisations, but builds on the idea of situated knowledge, which in turn requires a pluralist methodology and an acceptance of fundamental uncertainty. Such a methodology allows for emergent identity, for the cognitive roles of emotion and social convention, and for attention to power other than market power. Reflecting on how limited is the scope for mainstream macroeconomics to address gender, and what is required of a useful alternative, a political economy approach provides a clear focus for a more general discussion of the future of macroeconomics from an evolutionary perspective.

Interaction of hydroxychloroquine with SARS-CoV2 functional proteins using all-atoms non-equilibrium alchemical simulations

Using a combination of enhanced sampling molecular dynamics techniques and non-equilibrium alchemical transformations with full atomistic details, we have shown that hydroxychloroquine (HCQ) may act as a mild inhibitor of important functional proteins for SARS-CoV2 replication, with potency increasing in the series PLpro, 3CLpro, RdRp. By analyzing the bound state configurations, we were able to improve the potency for the 3CLpro target, designing a novel HCQ-inspired compound, named PMP329, with predicted nanomolar activity. If confirmed in vitro, our results provide a molecular rationale for the use of HCQ or of strictly related derivatives in the treatment of Covid-19.

System analysis of the nonequilibrium conditions of peritectic transformation for Fe-C-∑X alloys

Abstract The authors present a computer model of the non-equilibrium peritectic transformation in the multi-component alloys Fe-C-∑Xi for the system analysis of phase transformations. The course of the process describes mesoscale equations of heat transfer, phase releasing, and diffusional redistribution of components under the coalescence of a dendritic structure. The simulation results for the rate of formation of the austenitic phase are compared to the literature data.

In-situ observation of an unusual phase transformation pathway with Guinier-Preston zone-like precipitates in Zr-based bulk metallic glasses

The pathway of amorphous-to-crystalline phase transformation in Zr52.5Cu17.9Ni14.6Al10Ti5 bulk metallic glasses was studied using a suite of in-situ techniques. Multi-scale structure evidence reveals a five-stage pathway, analogous to the non-equilibrium transformation process with Guinier-Preston zones during aging in precipitation-hardened alloys, by the following sequence upon isothermal annealing the alloy in the supercooled liquid region: polyamorphous phase transition, chemical phase separation, the formation of a poorly-ordered metastable phase, and the formation of a final crystalline product. The changeable incubation periods at different annealing temperatures, and the abrupt multi-scale structure changes, as well as a latent heat release in the calorimetric measurements, support the first-order nature of the phase transformation at early stages. The structure evolution in real-space indicates that the enhancement of cluster connectivity on the medium-range scale plays essential roles in the early stages of the phase transformation, while the interface-limited ordering dominates the later stages. The experimental results suggest the phase transformation pathway with “Guinier-Preston zone-like” precipitates accompanied by the kinematic development of core-shell structures of diffuse interfaces with order parameters gradients, enabling the step-by-step decrease of free energy of the alloy system during phase transformation, which might be a characteristic behavior for multicomponent Zr-based alloys with excellent glass-forming ability.

A Nonequilibrium Variational Polaron Theory to Study Quantum Heat Transport

We propose a nonequilibrium variational polaron transformation, based on an ansatz for nonequilibrium steady state (NESS) with an effective temperature, to study quantum heat transport at the nanoscale. By combining the variational polaron transformed master equation with the full counting statistics, we have extended the applicability of the polaron-based framework to study nonequilibrium process beyond the super-Ohmic bath models. Previously, the polaron-based framework for quantum heat transport reduces exactly to the non-interacting blip approximation (NIBA) formalism for Ohmic bath models due to the issue of the infrared divergence associated with the full polaron transformation. The nonequilibrium variational method allows us to appropriately treat the infrared divergence in the low-frequency bath modes and explicitly include cross-bath correlation effects. These improvements provide more accurate calculation of heat current than the NIBA formalism for Ohmic bath models. We illustrate the aforementioned improvements with the nonequilibrium spin-boson model in this work and quantitatively demonstrate the cross-bath correlation, current turnover, and rectification effects in quantum heat transfer.

Role of coherence in the nonequilibrium thermodynamics of quantum systems.

Exploiting the relative entropy of coherence, we isolate the coherent contribution in the energetics of a driven nonequilibrium quantum system. We prove that a division of the irreversible work can be made into a coherent and incoherent part. This provides an operational criterion for quantifying the coherent contribution in a generic nonequilibrium transformation on a closed quantum system. We then study such a contribution in two physical models of a driven qubit and kicked rotor. In addition, we also show that coherence generation is connected to the nonadiabaticity of a processes, for which it gives the dominant contribution for slow-enough transformations. The amount of generated coherence in the energy eigenbasis is equivalent to the change in diagonal entropy, and here we show that it fulfills a fluctuation theorem.