Microscopic Dynamics Research Articles

Muonium state exchange dynamics in n -type GaAs

Muonium (Mu), a pseudoisotope of hydrogen with a positively charged muon in place of the proton, takes the form Mu+,0,− (like isolated hydrogen, i.e., H+,0,−) in semiconductors. The specifics of the charge state depend on the local electronic environment of the host. After initial muon implantation, generated Mu centers interact with free charge carriers and electronic spins, transition between sites, and form a dynamic network of state exchange. We identified the model of Mu dynamics in n-type GaAs using the density matrix simulation method and photoexcited muon spin spectroscopy technique. Fitting to the dark and illuminated μSR data provided transition rates between Mu states, revealing the underlying mechanisms at play between the Mu centers (cf. isolated H) and the host. Deduced capture/scattering cross sections of the Mu states reflected the microscopic dynamics of Mu. Illumination studies enabled us to measure interactions between Mu and minority carriers, which would be unavailable in dark measurements without heating. The methodology developed in this study may be applied to other semiconductor systems for a deeper understanding of the Mu state exchange dynamics. Published by the American Physical Society 2024

Thermodynamic Bounds on Generalized Transport: From Single-Molecule to Bulk Observables.

We prove that the transport of any differentiable scalar observable in d-dimensional nonequilibrium systems is bounded from above by the total entropy production scaled by the amount the observation "stretches" microscopic coordinates. The result-a time-integrated generalized speed limit-reflects the thermodynamic cost of transport of observables, and places underdamped and overdamped stochastic dynamics on equal footing with deterministic motion. Our work allows for stochastic thermodynamics to make contact with bulk experiments, and fills an important gap in thermodynamic inference, since microscopic dynamics is, at least for short times, underdamped. Requiring only averages but not sample-to-sample fluctuations, the proven transport bound is practical and applicable not only to single-molecule but also bulk experiments where only averages are observed, which we demonstrate by examples. Our results may facilitate thermodynamic inference on molecular machines without an obvious directionality from bulk observations of transients probed, e.g., in time-resolved x-ray scattering.

Uncovering the phonon spectra and lattice dynamics of plastically deformable InSe van der Waals crystals

Stacking two-dimensional (2D) van der Waals (vdW) materials in a layered bulk structure provides an appealing platform for the emergence of exotic physical properties. As a vdW crystal with exceptional plasticity, InSe offers the opportunity to explore various effects arising from the coupling of its peculiar mechanical behaviors and other physical properties. Here, we employ neutron scattering techniques to investigate the correlations of plastic interlayer slip, lattice anharmonicity, and thermal transport in InSe crystals. Not only are the interlayer slip direction and magnitude well captured by shifts in the Bragg reflections, but we also observe a deviation from the expected Debye behaviour in the heat capacity and lattice thermal conductivity. Combining the experimental data with first-principles calculations, we tentatively attribute the observed evidence of strong phonon-phonon interactions to a combination of a large acoustic-optical frequency resonance and a nesting effect. These findings correlate the macroscopic plastic slip and the microscopic lattice dynamics, providing insights into the mechano-thermo coupling and modulation in 2D vdW materials.

Information-theoretical limit on the estimates of dissipation by molecular machines using single-molecule fluorescence resonance energy transfer experiments.

Single-molecule fluorescence resonance energy transfer (FRET) experiments are commonly used to study the dynamics of molecular machines. While in vivo molecular processes often break time-reversal symmetry, the temporal directionality of cyclically operating molecular machines is often not evident from single-molecule FRET trajectories, especially in the most common two-color FRET studies. Solving a more quantitative problem of estimating the energy dissipation/entropy production by a molecular machine from single-molecule data is even more challenging. Here, we present a critical assessment of several practical methods of doing so, including Markov-model-based methods and a model-free approach based on an information-theoretical measure of entropy production that quantifies how (statistically) dissimilar observed photon sequences are from their time reverses. The Markov model approach is computationally feasible and may outperform model free approaches, but its performance strongly depends on how well the assumed model approximates the true microscopic dynamics. Markov models are also not guaranteed to give a lower bound on dissipation. Meanwhile, model-free, information-theoretical methods systematically underestimate entropy production at low photoemission rates, and long memory effects in the photon sequences make these methods demanding computationally. There is no clear winner among the approaches studied here, and all methods deserve to belong to a comprehensive data analysis toolkit.

Interpretation of quantum theory in a cosmological perspective

We reconsider the problem of the interpretation of the quantum theory (QT) in the perspective of the entire universe and of the Bohr's idea that the classical language is the language of our experience and QT acquires a meaning only with a reference to it. We distinguish a classical or macroscopic state, and a quantum or microscopic one that is perceived only through the modifications that it induces in the first. The macroscopic state is specified by a set of variables, a classical energy–momentum tensor and conserved currents, which are supposed to have always a well-defined value. The microscopic state and dynamics are expressed by the usual QT formalism. For the macroscopic variables, a basic distribution of probability is postulated in terms of quantum operators and a statistical operator, what replace the usual probability rule of QT. For the universe, a variance of the ΛCDM model with Ω=1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Omega = 1$$\\end{document} is assumed, one inflaton, a Goldstone type potential, initial time at t=-∞\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$t = - \\infty$$\\end{document}, expectation values of all fundamental fields vanishing for t→-∞\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$t \ o - \\infty$$\\end{document}. The scalar fluctuations in the cosmic microwave background is correctly explained, but the absence of the tensor fluctuations remains not understood. This seems to suggest that gravity is a pure classical phenomenon what perhaps could be accommodated in our framework.

Chiral dynamics in soft triaxial nuclei

The chirality in soft triaxial nuclei is investigated for the first time with the time-dependent and tilted axis cranking covariant density functional theories on a three-dimensional space lattice in a microscopic and self-consistent way. Taking the puzzling chiral nucleus 106Ag as an example, the experimental energies of the observed nearly degenerate bands are well reproduced without any free parameters beyond the well-defined density functional. A novel chiral mode in soft triaxial nuclei is newly revealed from the microscopic dynamics of the total angular momentum. This opens a new research area for the study of chirality, particularly in relation to soft nuclear shapes.

AI-NERD: Elucidation of relaxation dynamics beyond equilibrium through AI-informed X-ray photon correlation spectroscopy

Understanding and interpreting dynamics of functional materials in situ is a grand challenge in physics and materials science due to the difficulty of experimentally probing materials at varied length and time scales. X-ray photon correlation spectroscopy (XPCS) is uniquely well-suited for characterizing materials dynamics over wide-ranging time scales. However, spatial and temporal heterogeneity in material behavior can make interpretation of experimental XPCS data difficult. In this work, we have developed an unsupervised deep learning (DL) framework for automated classification of relaxation dynamics from experimental data without requiring any prior physical knowledge of the system. We demonstrate how this method can be used to accelerate exploration of large datasets to identify samples of interest, and we apply this approach to directly correlate microscopic dynamics with macroscopic properties of a model system. Importantly, this DL framework is material and process agnostic, marking a concrete step towards autonomous materials discovery.

Multiscale chemogenetic dissection of fronto-temporal top-down regulation for object memory in primates

Visual object memory is a fundamental element of various cognitive abilities, and the underlying neural mechanisms have been extensively examined especially in the anterior temporal cortex of primates. However, both macroscopic large-scale functional network in which this region is embedded and microscopic neuron-level dynamics of top-down regulation it receives for object memory remains elusive. Here, we identified the orbitofrontal node as a critical partner of the anterior temporal node for object memory by combining whole-brain functional imaging during rest and a short-term object memory task in male macaques. Focal chemogenetic silencing of the identified orbitofrontal node downregulated both the local orbitofrontal and remote anterior temporal nodes during the task, in association with deteriorated mnemonic, but not perceptual, performance. Furthermore, imaging-guided neuronal recordings in the same monkeys during the same task causally revealed that orbitofrontal top-down modulation enhanced stimulus-selective mnemonic signal in individual anterior temporal neurons while leaving bottom-up perceptual signal unchanged. Furthermore, similar activity difference was also observed between correct and mnemonic error trials before silencing, suggesting its behavioral relevance. These multifaceted but convergent results provide a multiscale causal understanding of dynamic top-down regulation of the anterior temporal cortex along the ventral fronto-temporal network underpinning short-term object memory in primates.

Measuring colloidomer hydrodynamics with holographic video microscopy.

In-line holographic video microscopy records a wealth of information about the microscopic structure and dynamics of colloidal materials. Powerful analytical techniques are available to retrieve that information when the colloidal particles are well separated. Large assemblies of close-packed particles create holograms that are substantially more challenging to interpret. We demonstrate that Rayleigh-Sommerfeld back propagation is useful for analyzing holograms of colloidomer chains, close-packed linear assemblies of micrometer-scale emulsion droplets. Colloidomers are fully flexible chains and undergo three-dimensional configurational changes under the combined influence of random thermal forces and hydrodynamic forces. We demonstrate the ability of holographic reconstruction to track these changes as colloidomers sediment through water in a horizontal slit pore. Comparing holographically measured configurational trajectories with predictions of hydrodynamic models both validates the analytical technique for this valuable class of self-organizing materials and also provides insights into the influence of geometric confinement on colloidomer hydrodynamics.

Unraveling relationship between complex lifetimes and microscopic diffusion in deep eutectic solvents.

Aqueous mixtures of deep eutectic solvents (DESs) have emerged as a subject of interest in recent years for their tailored physicochemical properties. However, a comprehensive understanding of water's multifaceted influence on the microscopic dynamics, including its impact on improved transport properties of the DES, remains elusive. Additionally, the diffusion mechanisms within DESs manifest heterogeneous behavior, intricately tied to the formation and dissociation kinetics of complexes and hydrogen bonds. Therefore, it is imperative to explore the intricate interplay between bond kinetics, diffusion mechanism, and dynamical heterogeneity. This work employs water as an agent to explore their relationships by studying various relaxation phenomena in a DES based on acetamide and lithium perchlorate over a wide range of water concentrations. Notably, acetamide exhibits Fickian yet non-Gaussian diffusion across all water concentrations with Fickian (τf) and Gaussian (τg) timescales following a power-law relationship, τg∝τfγ, γ ∼ 1.4. The strength of coupling between bond kinetics and different diffusion timescales is estimated through various power-law relationships. Notably, acetamide-water hydrogen bond lifetime is linked to diffusive timescales through a single power-law over the entire water concentration studied. However, the relationship between diffusive timescales and the lifetime of acetamide-lithium complexes shows a sharp transition in behavior at 20 wt. % water, reflecting a change from vehicular diffusion below this concentration to structural diffusion above it. Our findings emphasize the critical importance of understanding bond dynamics within DESs, as they closely correlate with and regulate the molecular diffusion processes within these systems.

Occurrence and Flow Behavior for Oil Transport in Mixed Wetting Nanoscale Shale Bedding Fractures.

Shale reservoirs are characterized by an abundance of nanoscale porosities and microfractures. The states of fluid occurrence and flow behaviors within nanoconfined spaces necessitate novel research approaches, as traditional percolation mathematical models are inadequate for accurately depicting these phenomena. This study takes the Gulong shale reservoir in China as the subject of its research. Initially, the unique mixed wetting characteristics of the Gulong shale reservoir are examined and characterized using actual micropore images. Subsequently, the occurrence and flow behavior of oil within the nanoscale bedding fractures under various wettability scenarios are described through a combination of microscopic pore image and molecular dynamics simulations. Ultimately, a mathematical model is established that depicts the velocity distribution of oil and its apparent permeability. This study findings indicate that when the scale of the shale bedding fractures is less than 100 nm, the impact of the nanoconfinement effect is significant and cannot be overlooked. In this scenario, the state of oil occurrence and its flow behavior are influenced by the initial oil-wet surface area on the mixed wetting walls. The study quantifies the velocity and density distribution of oil in mixed wetting nanoscale shale bedding fractures through a mathematical model, providing a crucial theoretical basis for upscaling from the nanoscale to the macroscale.

Mechanisms of interface electrostatic potential induced asphalt-aggregate adhesion

The electrostatic potential at the interface of the asphalt molecular and aggregate oxides is the primary factor generating the adhesion between the asphalt-aggregate contact surfaces. However, the route of electrostatic potential affecting the asphalt-aggregate adhesion is yet to be determined at the molecular level. This study proposed that the electron accumulation at the interface of the asphalt molecular and aggregate oxides generates a significant electrostatic potential hence to induce the adhesion between the asphalt and aggregate in asphalt pavement. A microscopic molecular dynamics (MD) simulation incorporated with macroscopic adhesion work experiments is conducted to analyze the interface adhesive performance between the asphalt and aggregate. The adhesion work experiment demonstrated the effect of aggregate surface oxides on asphalt adhesion at the macro level and further verified the simulation results. The result demonstrated that a notable electron accumulation can be observed by MD at the interface of asphalt molecular and multiple oxides which generates the electrostatic potential. The strong electrostatic attractions and hydrogen bonds between alkaline oxides (MgO, CaO, CaCO3) and asphalt molecules enhance the relative concentration distribution, diffusion coefficient, and adhesion of asphalt on the aggregate surface. The significant electrostatic potential difference at the interface of the asphalt molecular and the oxide enables a strong adhesion between them due to the near-surface failure potential. Besides, the negative charge accumulation on both the benzene ring structure and oxygen atoms in the asphalt molecules results in poor adhesion at the interface of asphalt molecules and multiple oxides. It was found that a high correlation exists between the MD prediction and experimental testing results. Thus, this research provides a valuable tool for guiding the pairing and selection of asphalt with various minerals for pavement design, construction, and maintenance agencies.

A review of advancements in theoretical simulation of oxygen reduction reaction and oxygen evolution reaction single-atom catalysts

Aqueous electrolytes metal-air batteries have garnered widespread attention owing to their safety, low cost, and non-toxic properties. Yet, their development is hindered by slow reaction efficiency. To address this issue, extensive exploratory work has been conducted by researchers. Among them, single-atom catalysts (SACs) represent a significant research direction and a hot topic for the metal-air battery catalysts. Theoretical calculations have been instrumental in predicting and screening high-activity SACs. Besides, the efforts have been made to investigate the performance of SACs for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, we specifically analyze the development and prospects of SACs for ORR/OER. The theoretical research on SACs can be divided into two stages. The first stage involves exploring the mechanism of ORR/OER reactions, also known as ideal condition theoretical simulations. The exploration scope can be categorized into four types: 1) transition metals loaded on different substrates; 2) different transition metals loaded on the same substrate; 3) the impact of the coordination environment on the catalytic efficacy of SACs; and 4) the application of machine learning in the field of catalysts. The second stage involves simulating experimental environments, where researchers begin to consider the effects of voltage, solvation, pH, surface states, and microscopic molecular dynamics on catalysts. This work comprehensively reviews the current status of SACs for ORR/OER and provides suggestions for the development of SACs in the next stage.

Space-resolved dynamic light scattering within a millimeter-sized drop: From Brownian diffusion to the swelling of hydrogel beads.

We present a dynamic light scattering setup to probe, with time and space resolution, the microscopic dynamics of soft matter systems confined within millimeter-sized spherical drops. By using an ad hoc optical layout, we tackle the challenges raised by refraction effects due to the unconventional shape of the samples. We first validate the setup by investigating the dynamics of a suspension of Brownian particles. The dynamics measured at different positions in the drop, and hence different scattering angles, are found to be in excellent agreement with those obtained for the same sample in a conventional light scattering setup. We then demonstrate the setup capabilities by investigating a bead made of a polymer hydrogel undergoing swelling. The gel microscopic dynamics exhibit a space dependence that strongly varies with time elapsed since the beginning of swelling. Initially, the dynamics in the periphery of the bead are much faster than in the core, indicative of nonuniform swelling. As the swelling proceeds, the dynamics slow down and become more spatially homogeneous. By comparing the experimental results to numerical and analytical calculations for the dynamics of a homogeneous, purely elastic sphere undergoing swelling, we establish that the mean square displacement of the gel strands deviates from the affine motion inferred from the macroscopic deformation, evolving from fast diffusivelike dynamics at the onset of swelling to slower, yet supradiffusive, rearrangements at later stages.

Chaotic route to classical thermalization: A real-space analysis.

Most of the previous studies on classical thermalization focus on the wave-vector space, encountering limitations when extended beyond quasi-integrable regions. In this study, we propose a scheme to study the thermalization of the classical Hamiltonian chain of interacting oscillators in real space by developing a thermalization indicator proposed by Parisi [Europhys. Lett. 40, 357 (1997)0295-507510.1209/epl/i1997-00471-9], which approaches zero in the thermal state. Upon reaching the steady state characterized by the generalized Gibbs ensemble for a harmonic chain, a quench protocol is implemented to change the Hamiltonian to a nonintegrable form instantaneously, thereby preparing nonequilibrium initial states. This approach enables investigations of thermalization in real space, particularly valuable for exploring regions beyond quasi-integrability. For the FPUT-β lattice, we observe that the thermalization time as a function of the nonintegrable strength follows a -2 scaling law in the quasi-integrable region and -1/4 in the strongly integrable region. Moreover, numerical results reveal the thermalization time is proportional to the Lyapunov time, which bridges microscopic chaotic dynamics and the macroscopic thermalization process.

Natural metric-affine inflation

We consider here natural inflation in the low energy (two-derivative) metric-affine theory containing only the minimal degrees of freedom in the inflationary sector, i.e. the massless graviton and the pseudo-Nambu-Goldstone boson (PNGB). This theory contains the Ricci-like and parity-odd Holst invariants together with non-minimal couplings between the PNGB and the above-mentioned invariants. The Palatini and Einstein-Cartan realizations of natural inflation are particular cases of our construction. Explicit models of this type featuring non-minimal couplings are shown to emerge from the microscopic dynamics of a QCD-like theory with an either sub-Planckian or trans-Planckian confining scale and that is renormalizable on Minkowski spacetime. Moreover, for these models, we find regions of the parameter space where the inflationary predictions agree with the most recent observations at the 2σ level. We find that in order to enter the 1σ region it is necessary (and sufficient) to have a finite value of the Barbero-Immirzi parameter and a sizable non-minimal coupling between the inflaton and the Holst invariant (with sign opposite to the Barbero-Immirzi parameter). Indeed, in this case the potential of the canonically normalized inflaton develops a plateau as shown analytically.

Thermodynamics of Irreversible Processes: Fundamental Constraints, Representations, and Formulation of Boundary Conditions

Starting from the analysis of the lack of positivity of the Cattaneo heat equation, this work addresses the thermodynamic relevance of the positivity constraint in irreversible thermodynamics, that is at least as significant as the entropic constraints. The fulfillment of this condition in hyperbolic models leads to the parametrization of the concentration fields with respect to internal variables associated with the microscopic dynamics. Using Brownian motion theory as a landmark example for deriving macroscopic transport equations from the equations of motion at the particle/molecular level, we discuss two typical problems involving hydrodynamic interactions at the microscale: surface chemical reactions at a solid interface of a diffusing reactant, and mass-balance equations in a complex viscoelastic fluid, in which the physics of the interaction leads either to overcoming the parabolic diffusion model or to considering the parametrization of the concentration with respect to the degrees of freedom associated with the relaxation dynamics of the solvent fluid.

On the Hydrodynamics of Active Matter Models on a Lattice

Active matter has been widely studied in recent years because of its rich phenomenology, whose mathematical understanding is still partial. We present some results, based on [8, 17] linking microscopic lattice gases to their macroscopic limit, and explore how the mathematical state of the art allows to derive from various types of microscopic dynamics their hydrodynamic limit. We present some of the crucial aspects of this theory when applied to weakly asymmetric active models. We comment on the speci fic challenges one should consider when designing an active lattice gas, and in particular underline math- ematical and phenomenological differences between gradient and non-gradient models. Our purpose is to provide the physics community, as well as member of the mathematical community not specialized in the mathematical derivation of scaling limits of lattice gases, some key elements in de ning microscopic models and deriving their hydrodynamic limit.

Scalable, ab initio protocol for quantum simulating SU(N)×U(1) Lattice Gauge Theories

We propose a protocol for the scalable quantum simulation of SU(N)×U(1) lattice gauge theories with alkaline-earth like atoms in optical lattices in both one- and two-dimensional systems. The protocol exploits the combination of naturally occurring SU(N) pseudo-spin symmetry and strong inter-orbital interactions that is unique to such atomic species. A detailed ab initio study of the microscopic dynamics shows how gauge invariance emerges in an accessible parameter regime, and allows us to identify the main challenges in the simulation of such theories. We provide quantitative results about the requirements in terms of experimental stability in relation to observing gauge invariant dynamics, a key element for a deeper analysis on the functioning of such class of theories in both quantum simulators and computers.

From creep to flow: Granular materials under cyclic shear

When unperturbed, granular materials form stable structures that resemble the ones of other amorphous solids like metallic or colloidal glasses. Whether or not granular materials under shear have an elastic response is not known, and also the influence of particle surface roughness on the yielding transition has so far remained elusive. Here we use X-ray tomography to determine the three-dimensional microscopic dynamics of two granular systems that have different roughness and that are driven by cyclic shear. Both systems, and for all shear amplitudes Γ considered, show a cross-over from creep to diffusive dynamics, indicating that rough granular materials have no elastic response and always yield, in stark contrast to simple glasses. For the system with small roughness, we observe a clear dynamic change at Γ ≈ 0.1, accompanied by a pronounced slowing down and dynamical heterogeneity. For the large roughness system, the dynamics evolves instead continuously as a function of Γ. We rationalize this roughness dependence using the potential energy landscape of the systems: The roughness induces to this landscape a micro-corrugation with a new length scale, whose ratio over the particle size is the relevant parameter. Our results reveal the unexpected richness in relaxation mechanisms for real granular materials.