Two-time Correlation Functions Research Articles

On the analysis of two-time correlation functions: equilibrium versus non-equilibrium systems

X-ray photon correlation spectroscopy (XPCS) is a powerful tool for the investigation of dynamics covering a broad range of timescales and length scales. The two-time correlation function (TTC) is commonly used to track non-equilibrium dynamical evolution in XPCS measurements, with subsequent extraction of one-time correlations. While the theoretical foundation for the quantitative analysis of TTCs is primarily established for equilibrium systems, where key parameters such as the diffusion coefficient remain constant, non-equilibrium systems pose a unique challenge. In such systems, different projections (`cuts') of the TTC may lead to divergent results if the underlying fundamental parameters themselves are subject to temporal variations. This article explores widely used approaches for TTC calculations and common methods for extracting relevant information from correlation functions, particularly in the light of comparing dynamics in equilibrium and non-equilibrium systems.

Aging properties of the voter model with long-range interactions

We investigate the aging properties of the one-dimensional voter model with long-range interactions in its ordering kinetics. In this system, an agent, Si=±1 , positioned at a lattice vertex i, copies the state of another one located at a distance r, selected randomly with a probability P(r)∝r−α . Employing both analytical and numerical methods, we compute the two-time correlation function G(r;t,s) ( t⩾s ) between the state of a variable Si at time s and that of another one, at distance r, at time t. At time t, the memory of an agent of its former state at time s, expressed by the autocorrelation function A(t,s)=G(r=0;t,s) , decays algebraically for α > 1 as [L(t)/L(s)]−λ , where L is a time-increasing coherence length and λ is the Fisher–Huse exponent. We find λ = 1 for α > 2, and λ=1/(α−1) for 1<α⩽2 . For α⩽1 , instead, there is an exponential decay, as in the mean field. Then, in contrast with what is known for the related Ising model, here we find that λ increases upon decreasing α. The space-dependent correlation G(r;t,s) obeys a scaling symmetry G(r;t,s)=g[r/L(s);L(t)/L(s)] for α > 2. Similarly, for 1<α⩽2 , one has G(r;t,s)=g[r/L(t);L(t)/L(s)] , where the length L regulating two-time correlations now differs from the coherence length as L∝Lδ , with δ=1+2(2−α) .

X-ray-induced piezoresponse during X-ray photon correlation spectroscopy of PbMg1/3Nb2/3O3.

X-ray photon correlation spectroscopy (XPCS) holds strong promise for observing atomic-scale dynamics in materials, both at equilibrium and during non-equilibrium transitions. Here an in situ XPCS study of the relaxor ferroelectric PbMg1/3Nb2/3O3 (PMN) is reported. A weak applied AC electric field generates strong response in the speckle of the diffuse scattering from the polar nanodomains, which is captured using the two-time correlation function. Correlated motions of the Bragg peak are also observed, which indicate dynamic tilting of the illuminated volume. This tilting quantitatively accounts for the observed two-time speckle correlations. The magnitude of the tilting would not be expected solely from the modest applied field, since PMN is an electrostrictive material with no linear strain response to the field. A model is developed based on non-uniform static charging of the illuminated surface spot by the incident micrometre-scale X-ray beam and the electrostrictive material response to the combination of static and dynamic fields. The model qualitatively explains the direction and magnitude of the observed tilting, and predicts that X-ray-induced piezoresponse could be an important factor in correctly interpreting results from XPCS and nanodiffraction studies of other insulating materials under applied AC field or varying X-ray illumination.

Quantum to Classical Cavity Chemistry Electrodynamics.

Polaritonic chemistry has ushered in new avenues for controlling molecular dynamics. However, two key questions remain: (i) Can classical light sources elicit the same effects as certain quantum light sources on molecular systems? (ii) Can semiclassical treatments of light-matter interactions capture nontrivial quantum effects observed in molecular dynamics? This work presents a quantum-classical approach addressing issues of realizing cavity chemistry effects without actual cavities. It also highlights the limitations of the standard semiclassical light-matter interaction. It is demonstrated that classical light sources can mimic quantum effects up to the second order of light-matter interaction provided that the mean-field contribution, the symmetrized two-time correlation function, and the linear response function are the same in both situations. Numerical simulations show that the quantum-classical method aligns more closely with exact quantum molecular-only dynamics for quantum light states such as Fock states, superpositions of Fock states, and vacuum squeezed states than does the conventional semiclassical approach.

Resonance fluorescence in Λ, V and Ξ - type three-level configurations

We theoretically study the resonance fluorescence spectra of the lambda (Λ), vee (V) and cascade (Ξ) type three-level configurations. It is shown that each system with two detuning frequencies can be modelled using the SU(3) symmetry group to derive a generalized optical Bloch equation. For each configuration, this equation is solved to calculate the two-time correlation function by invoking the quantum regression theorem. The incoherent part of the power spectra gives the characteristic multi-peak fluorescence profiles which are different for different configurations. We also discuss how the dressed-state structure of such system can explain the origin of quintuplet profile of the fluorescent spectrum.

Dynamical symmetries in the non-equilibrium dynamics of the directed spherical model

The dynamical scaling and ageing in the relaxational dynamics of the quenched directed spherical model is analysed. The exact two-time correlation and response functions display new regimes of ballistic or anisotropic ballistic scaling, at larger distances than probed in the usual regime of diffusive scaling. The role of long-ranged initial correlations on the existence of these scaling regimes is clarified. Their dynamical symmetries are described in terms of extensions of the Schrödinger algebra appropriate to non-equilibrium dynamics in that the anisotropic ballistic scaling regime can be interpreted in terms of meta-Schrödinger invariance while the regime of isotropic ballistic scaling is meta-conformally invariant.

Beam Effects on Atomic Dynamics in Metallic Glasses Studied With Electron Correlation Microscopy.

Electron correlation microscopy (ECM) is used to investigate atomic dynamics in metallic glasses (MG) close to metastable equilibrium. It temporally correlates diffracted intensities of a time series of dark-field images to deduce a metric for structural decays. The measurement parameters, such as time and temperature, must be chosen according to the material of interest. In this work, ECM was extended to measurements at room temperature. To ensure, or select, a time window with quasi-thermodynamic equilibrium/steady-state measurement conditions, two-time correlation functions of diffracted intensities were calculated. The dynamics at room temperature are partly driven by the electron beam, thus affecting the material and the results. A systematic analysis of the influence of the electron beam is presented, revealing an inverse relation between electron dose rate and intensity correlation decay times at 300 kV acceleration voltage. However, the underlying dynamical mechanisms, described by a stretching exponent, are found to be independent of the applied electron dose rate for a Pd40Ni40P20 MG. An extrapolation of the results to infinite long measurement times and zero dose rate agrees with X-ray photon correlation spectroscopy data and justifies the application of beam-driven ECM at room temperature to study the dynamics of disordered systems.

Phonon Signatures in Photon Correlations.

We show that the second-order, two-time correlation functions for phonons and photons emitted from a vibronic molecule in a thermal bath result in bunching and antibunching (a purely quantum effect), respectively. Signatures relating to phonon exchange with the environment are revealed in photon-photon correlations. We demonstrate that cross-correlation functions have a strong dependence on the order of detection giving insight into how phonon dynamics influences the emission of light. This work offers new opportunities to investigate quantum effects in condensed-phase molecular systems.

Growth and aging in a few phase-separating active matter systems.

Via computer simulations we study evolution dynamics in systems of continuously moving active Brownian particles. The obtained results are discussed against those from the passive 2D Ising case. Following sudden quenches of random configurations to state points lying within the miscibility gaps and to the critical points, we investigate the far-from-steady-state dynamics by calculating quantities associated with structure and characteristic length scales. We also study aging for quenches into the miscibility gap and provide a quantitative picture for the scaling behavior of the two-time order-parameter correlation function. The overall structure and dynamics are consistent with expectations from the Ising model. This remains true for certain active lattice models as well, for which we present results for quenches to the critical points.

Entanglement and thermokinetic uncertainty relations in coherent mesoscopic transport

A deeper understanding of the differences between quantum and classical dynamics promises great potential for emerging technologies. Nevertheless, some aspects remain poorly understood, particularly concerning the role of quantum coherence in open quantum systems. On the one hand, coherence leads to entanglement and even nonlocality. On the other, it may lead to a suppression of fluctuations, causing violations of thermo-kinetic uncertainty relations (TUR and KUR) that are valid for classical processes. These represent two different manifestations of coherence, one depending only on the state of the system (static) and one depending on two-time correlation functions (dynamical). Here we employ these manifestations of coherence to determine when mesoscopic quantum transport can be captured by a classical model based on stochastic jumps, and when such a model breaks down, implying nonclassical behavior. To this end, we focus on a minimal model of a double quantum dot coupled to two thermal reservoirs. In this system, quantum tunneling induces Rabi oscillations and results in both entanglement and nonlocality, as well as TUR and KUR violations. These effects, which describe the breakdown of a classical description, are accompanied by a peak in coherence. Our results provide guiding principles for the design of out-of-equilibrium devices that exhibit nonclassical behavior.

Effusion of stochastic processes on a line

We consider the problem of leakage or effusion of an ensemble of independent stochastic processes from a region where they are initially randomly distributed. The case of Brownian motion, initially confined to the left half line with uniform density and leaking into the positive half line is an example which has been extensively studied in the literature. Here we derive new results for the average number and variance of the number of leaked particles for arbitrary Gaussian processes initially confined to the negative half line and also derive its joint two-time probability distribution, both for the annealed and the quenched initial conditions. For the annealed case, we show that the two-time joint distribution is a bivariate Poisson distribution. We also discuss the role of correlations in the initial particle positions on the statistics of the number of particles on the positive half line. We show that the strong memory effects in the variance of the particle number on the positive real axis for Brownian particles, seen in recent studies, persist for arbitrary Gaussian processes and also at the level of two-time correlation functions.

Coherent X-ray Scattering Reveals Nanoscale Fluctuations in Hydrated Proteins.

Hydrated proteins undergo a transition in the deeply supercooled regime, which is attributed to rapid changes in hydration water and protein structural dynamics. Here, we investigate the nanoscale stress-relaxation in hydrated lysozyme proteins stimulated and probed by X-ray Photon Correlation Spectroscopy (XPCS). This approach allows us to access the nanoscale dynamics in the deeply supercooled regime (T = 180 K), which is typically not accessible through equilibrium methods. The observed stimulated dynamic response is attributed to collective stress-relaxation as the system transitions from a jammed granular state to an elastically driven regime. The relaxation time constants exhibit Arrhenius temperature dependence upon cooling with a minimum in the Kohlrausch-Williams-Watts exponent at T = 227 K. The observed minimum is attributed to an increase in dynamical heterogeneity, which coincides with enhanced fluctuations observed in the two-time correlation functions and a maximum in the dynamic susceptibility quantified by the normalized variance χT. The amplification of fluctuations is consistent with previous studies of hydrated proteins, which indicate the key role of density and enthalpy fluctuations in hydration water. Our study provides new insights into X-ray stimulated stress-relaxation and the underlying mechanisms behind spatiotemporal fluctuations in biological granular materials.

Phonon blockade in a quadratically coupled optomechanical system with two-phonon driving

We propose a scheme to enhance phonon blockade effect in a quadratically coupled optomechanical system. By applying a degenerate parametric drive to the mechanical oscillator, we introduce a mechanical parametric amplifier (MPA) to the system. We show that the phonon blockade can be achieved in both the single-phonon resonant regime and multipath interference regime due to the optomechanical nonlinearity and MPA. By combining the two regimes together, we show that the phonon blockade effect is enhanced compared to the regime without MPA. What is more, the two-time second-order correlation function gradually tends to one without rapid oscillations in our scheme, which suggests that high time resolution is not necessary in the detection.

Non-Perturbative Treatment of Open-System Multi-Time Expectation Values in Gaussian Bosonic Environments

We determine the conditions for the equivalence between the multi-time expectation values of a general finite-dimensional open quantum system when interacting with, respectively, an environment undergoing a free unitary evolution or a discrete environment under a free evolution fixed by a proper Gorini-Kossakowski-Lindblad-Sudarshan generator. We prove that the equivalence holds if both environments are bosonic and Gaussian and if the one- and two-time correlation functions of the corresponding interaction operators are the same at all times. This result leads to a non-perturbative evaluation of the multi-time expectation values of operators and maps of open quantum systems interacting with a continuous set of bosonic modes by means of a limited number of damped modes, thus setting the ground for the investigation of open-system multi-time quantities in fully general regimes.

Machine Learning for analysis of speckle dynamics: quantification and outlier detection

X-ray photon correlation spectroscopy (XPCS) provides an understanding of complex dynamics in materials that are tied to their synthesis, properties, and behaviors. Analysis of XPCS data for dynamics that are far from equilibrium is labor intense and often can impede the discovery process, especially in experiments with high collection rates. Moreover, binning and averaging, involved in the analysis for alleviating poor signal-to-noise ratio, leads to a loss of temporal resolution and the accumulation of systematic error for the parameters quantifying the dynamics. Here, we integrate a denoising autoencoder model into workflows for the analysis of nonequilibrium two-time intensity-intensity correlation functions. Noise reduction allows for extracting the parameters that characterize the sample's dynamics with the temporal resolution limited only by frame rates. Not only does it improve the quantitative usage of the data, but it also creates the potential for automating the analytical workflow, which is a key to high-throughput or autonomous XPCS experiments. Various approaches for the uncertainty quantification and extension of the model for anomalies' detection are discussed.

Controlling Resonance Fluorescence Spectra and Photon Statistics in a Driven V-Type Quantum Emitter—Metal Nanoparticle Coupled Structure

We study the resonant fluorescence emission spectrum and the intensity-intensity correlations of the emitted fluorescent field by a V-type quantum emitter (QE) which is located near a metal nanosphere. For the description of the studied phenomena, we use the density matrix equations methodology combined with electromagnetic calculations and obtain results for the profile of the resonant fluorescence spectrum and the second-order correlation functions associated with the fluorescent photons. The decay rates and the coupling term exhibit a strong dependence on the distance that separates the QE from the metal nanoparticle. This distance also influences the resonance fluorescence of the V-type QE. We find that, in the general case, the resonant fluorescence spectrum is composed of five Lorentzian-type peaks, for high interparticle distances, while, when the QE is located very close to the surface of the nanosphere, the central resonance becomes dominant, and a single-peaked spectral profile appears. The two-time correlation functions of the fluorescent photons evolve in an oscillatory manner around unity, for non-zero time delay, with a period that decreases with the increase of the field intensity. In the strong driving field regime, the antibunching to bunching crossing time does not depend on the interparticle distance, contrary to the results found in the weak driving field regime. We also find that, for a weak laser field and under specific conditions, the second-order correlation functions constantly remain in the antibunching region.

Quantum regression theorem for multi-time correlators: A detailed analysis in the Heisenberg picture

The quantum regression theorem is one of the central results in open quantum systems and is extensively used for computing multi-point correlation functions. Traditionally it is derived for two-time correlators in the Markovian limit employing the Schr\"odinger picture. In this paper we make use of the Heisenberg picture to derive the quantum regression theorems for multi-time correlation functions, which in the special limit reduce to the well-known two-time regression theorem. For the multi-time correlation function we find that the regression theorem takes the same form as it takes for the two-time correlation function with a mild restriction that one of the times should be greater than all other time variables. Interestingly, the Heisenberg picture also allows us to derive an analog of regression theorem for out-of-time-ordered correlators. We further extend our study for the case of non-Markovian dynamics and report the modifications to the standard quantum regression theorem. We illustrate all of the above results using the paradigmatic dissipative spin-boson model.

Classical versus quantum intensity-field correlations of scattered light from extended cold atomic clouds

We calculate the intensity-field correlations in the light scattered by $N$ cold atoms driven by a quasiresonant laser field. Fundamental differences occur if the atomic state is an entangled single-excitation state or a coherent factorized state. We provide analytic expressions for the two-time field and intensity correlation functions for the timed Dicke state and the quasi-Bloch state. The comparison with multiatom simulations shows good agreement between numerical and analytic solutions.

Taylor's frozen-in hypothesis for magnetohydrodynamic turbulence and solar wind

In hydrodynamics, Taylor's frozen-in hypothesis connects the wavenumber spectrum to the frequency spectrum of a time series measured in real space. In this paper, we generalize Taylor's frozen-in hypothesis to magnetohydrodynamic turbulence. We analytically derive one-point two-time correlation functions for Elsässer variables whose Fourier transform yields the corresponding frequency spectra, E±(f). We show that for isotropic turbulence, E±(f)∝|U0 ∓ B0|2/3 in the Kolmogorov-like model and E±(f)∝(B0|U0 ∓ B0|)1/2 in the Iroshnikov–Kraichnan model, where U0 and B0 are the mean velocity and mean magnetic fields, respectively, and f±=k|U0 ∓ B0|/(2π) are the respective frequencies for a wavenumber k. However, for anisotropic magnetohydrodynamic turbulence, E±(f)∝B02/3 when U0≪B0. These results are important for the analysis of solar wind, in particular, those measured by Parker Solar Probe.

Nanofocused x-ray photon correlation spectroscopy

Here, we demonstrate an experimental proof of concept for nanofocused x-ray photon correlation spectroscopy, a technique sensitive to nanoscale fluctuations present in a broad range of systems. The experiment, performed at the NanoMAX beamline at MAX IV, uses a novel event-based x-ray detector to capture nanoparticle structural dynamics with microsecond resolution. By varying the nanobeam size from σ=88 nm to σ=2.5μm, we quantify the effect of the nanofocus on the small-angle scattering lineshape and on the diffusion coefficients obtained from nano-XPCS. We observe that the use of nanobeams leads to a multifold increase in speckle contrast, which greatly improves the experimental signal-to-noise ratio, quantified from the two-time intensity correlation functions. We conclude that it is possible to account for influence of the high beam divergence on the lineshape and measured dynamics by including a convolution with the nanobeam profile in the model.Received 17 December 2021Revised 19 May 2022Accepted 16 June 2022DOI:https://doi.org/10.1103/PhysRevResearch.4.L032012Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Physical SystemsNanoparticlesSynchrotron radiation & free-electron lasersTechniquesCoherent X-ray scatteringX-ray photon correlation spectroscopyCondensed Matter, Materials & Applied PhysicsPolymers & Soft Matter