Fluctuation-dissipation Theorem Research Articles

Statistics of protein electrostatics.

Molecular dynamics simulations of a small redox-active protein plastocyanin address two questions. (i) Do protein electrostatics equilibrate to the Gibbsian ensemble? (ii) Do the electrostatic potential and electric field inside proteins follow the Gaussian distribution? The statistics of electrostatic potential and electric field are probed by applying small charge and dipole perturbations to different sites within the protein. Nonergodic (non-Gibbsian) sampling is detectable through violations of exact statistical rules constraining the first and second statistical moments (fluctuation-dissipation relations) and the linear relation between free-energy surfaces of the collective coordinate representing the Hamiltonian electrostatic perturbation. We find weakly nonergodic statistics of the electrostatic potential (simulation time of 0.4-1.0 μs) and non-Gibbsian and non-Gaussian statistics of the electric field. A small dipolar perturbation of the protein results in structural instabilities of the protein-water interface and multi-modal distributions of the Hamiltonian energy gap. The variance of the electrostatic potential passes through a crossover at the glass transition temperature Ttr ≃ 170 K. The dipolar susceptibility, reflecting the variance of the electric field inside the protein, strongly increases, with lowering temperature, followed by a sharp drop at Ttr. The linear relation between free-energy surfaces can be directly tested by combining absorption and emission spectra of optical dyes. It was found that the statistics of the electrostatic potential perturbation are nearly Gibbsian/Gaussian, with little deviations from the prescribed statistical rules. On the contrary, the (nonergodic) statistics of dipolar perturbations are strongly non-Gibbsian/non-Gaussian due to structural instabilities of the protein hydration shell.

Stable-to-unstable transition in quantum friction

We investigate the frictional force arising from quantum fluctuations when two dissipative metallic plates are set in a shear motion. While early studies showed that the electromagnetic fields in the quantum friction setup reach nonequilibrium steady states, yielding a time-independent force, other works have demonstrated the failure to attain steady states, leading to instability and time-varying friction under sufficiently low-loss conditions. Here, we develop a fully quantum-mechanical theory without perturbative approximations, and we unveil the transition from stable to unstable regimes of the quantum friction setup. Due to the relative motion of the plates, their electromagnetic response may be active in some conditions, resulting in optical gain. We prove that the standard fluctuation-dissipation leads to inconsistent results when applied to our system, and, in particular, it predicts a vanishing frictional force. Using a modified fluctuation-dissipation relation tailored for gain media, we calculate the frictional force in terms of the system Green's function, thereby recovering early works on quantum friction. Remarkably, we also find that the frictional force diverges to infinity as the relative velocity of the plates approaches a threshold. This threshold is determined by the damping strength and the distance between the metal surfaces. Beyond this critical velocity, the system exhibits instability, akin to the behavior of a laser cavity, where no steady state exists. In such a scenario, the frictional force escalates exponentially. Our findings pave the way for experimental exploration of the frictional force in proximity to this critical regime. Published by the American Physical Society 2024

Generalized Langevin dynamics for single beads in linear elastic networks

We derive generalized Langevin equations (GLEs) for single beads in linear elastic networks. In particular, the derivations of the GLEs are conducted without employing normal modes, resulting in two distinct representations in terms of resistance and mobility kernels. The fluctuation-dissipation relations are also confirmed for both GLEs. Subsequently, we demonstrate that these two representations are interconnected via Laplace transforms. Furthermore, another GLE is derived by utilizing a projection operator method, and it is shown that the equation obtained through the projection scheme is consistent with the GLE with the resistance kernel. As simple examples, the general theory is applied to the Rouse model and the ring polymer, where the GLEs with the resistance and mobility kernels are explicitly derived for arbitrary positions of the tagged bead in these models. Finally, the GLE with the mobility kernel is also derived for the elastic network with hydrodynamic interactions under the pre-averaging approximation. ©2024 American Physical Society 2024 American Physical Society

Effective modeling of open quantum systems by low-rank discretization of structured environments.

The accurate description of the interaction of a quantum system with its environment is a challenging problem ubiquitous across all areas of physics and lies at the foundation of quantum mechanics theory. Here, we pioneer a new strategy to create discrete low-rank models of the system-environment interaction, by exploiting the frequency and time domain information encoded in the fluctuation-dissipation relation connecting the system-bath correlation function and the spectral density. We demonstrate the effectiveness of our methodology by combining it with tensor-network methodologies and simulating the quantum dynamics of complex excitonic systems in a highly structured bosonic environment. The new modeling framework sets the basis for a leap in the analysis of open quantum systems, providing controlled accuracy at significantly reduced computational costs, with benefits in all connected research areas.

Radiative-conductive heat transfer dynamics in dissipative dispersive anisotropic media

Abstract We develop a self-consistent theoretical formalism to model the dynamics of heat transfer in dissipative, dispersive, anisotropic nanoscale media, such as metamaterials. We employ our envelope dyadic Green’s function method to solve Maxwell’s macroscopic equations for the propagation of fluctuating electromagnetic fields in these media. We assume that the photonic radiative heat transfer mechanism in these media is complemented by dynamic phononic mechanisms of heat storage and conduction, accounting for effects of local heat generation. By employing the Poynting theorem and the fluctuation-dissipation theorem, we derive novel closed-form expressions for the radiative heat flux and the coupling term of photonic and phononic subsystems, which contains the heating rate and the radiative heat power contributions. We apply our formalism to the paraxial heat transfer in uniaxial media and present relevant closed-form expressions. By considering a Gaussian transverse temperature profile, we also obtain and solve a system of integro-differential heat diffusion equations to model the paraxial heat transfer in uniaxial reciprocal media. By applying the developed analytical model to radiative-conductive heat tranfer in nanolayered media constructed by layers of silica and germanium, we compute the temperature profiles for the three first orders of expansion and the total temperature profile as well. The results of this research can be of interest in areas of science and technology related to thermophotovoltaics, energy harvesting, radiative cooling, and thermal management at micro- and nanoscale.

Fock space and field theoretic description of nonequilibrium work relations

Abstract We consider classical, interacting particles coupled to a thermal reservoir and subject to a local, time-varying potential while undergoing hops on a lattice. We impose detailed balance on the hopping rates and map the dynamics to the Fock space Doi representation, from which we derive the Jarzynski and Crooks relations. Here the local potential serves to drive the system far from equilibrium and to provide the work. Next, we utilize the coherent state representation to map the system to a Doi–Peliti field theory and take the continuum limit. We demonstrate that time reversal in this field theory takes the form of a gauge-like transformation which leaves the action invariant up to a generated work term. The time-reversal symmetry leads to a fundamental identity, from which we are able to derive the Jarzynski and Crooks relations, as well as a far-from-equilibrium generalization of the fluctuation-dissipation relation.

Spin relaxation dynamics with a continuous spin environment: The dissipaton equation of motion approach.

We investigate the quantum dynamics of a spin coupling to a bath of independent spins via the dissipaton equation of motion (DEOM) approach. The bath, characterized by a continuous spectral density function, is composed of spins that are independent level systems described by the su(2) Lie algebra, representing an environment with a large magnitude of anharmonicity. Based on the previous work by Suarez and Silbey [J. Chem. Phys. 95, 9115 (1991)] and by Makri [J. Chem. Phys. 111, 6164 (1999)] that the spin bath can be mapped to a Gaussian environment under its linear response limit, we use the time-domain Prony fitting decomposition scheme to the bare-bath time correlation function (TCF) given by the bosonic fluctuation-dissipation theorem to generate the exponential decay basis (or pseudo modes) for DEOM construction. The accuracy and efficiency of this strategy have been explored by a variety of numerical results. We envision that this work provides new insights into extending the hierarchical equations of motion and DEOM approach to certain types of anharmonic environments with arbitrary TCF or spectral density.

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

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

Spectral eigenfunction decomposition of a Fokker–Planck operator for relativistic heavy-ion collisions

A spectral solution method is proposed to solve a previously developed non-equilibrium statistical model describing partial thermalization of produced charged hadrons in relativistic heavy-ion collisions, thus improving the accuracy of the numerical solution. The particle’s phase-space trajectories are treated as a drift-diffusion stochastic process, leading to a Fokker–Planck equation (FPE) for the single-particle probability distribution function. The drift and diffusion coefficients are derived from the expected asymptotic states via appropriate fluctuation–dissipation relations, and the resulting FPE is then solved numerically using a spectral eigenfunction decomposition. The calculated time-dependent particle distributions are compared to Pb–Pb data from the ATLAS and ALICE collaborations at the Large Hadron Collider.

White dwarf eccentricity fluctuation and dissipation by AGB convection

ABSTRACT Millisecond pulsars with white dwarf companions have typical eccentricities $e\sim 10^{-6}{\!-\!}10^{-3}$. The eccentricities of helium white dwarfs are explained well by applying the fluctuation–dissipation theorem to convective eddies in their red giant progenitors. We extend this theory to more massive carbon–oxygen (CO) white dwarfs with asymptotic giant branch (AGB) progenitors. Due to the radiation pressure in AGB stars, the dominant factor in determining the remnant white dwarf’s eccentricity is the critical residual hydrogen envelope mass $m_{\rm env}$ required to inflate the star to giant proportions. Using a suite of mesa stellar evolution simulations with $\Delta m_{\rm c}=10^{-3}\, {\rm M}_{\odot }$ core-mass intervals, we resolved the AGB thermal pulses and found that the critical $m_{\rm env}\propto m_{\rm c}^{-6}$. The resulting eccentricity $e\sim 3\times 10^{-3}$ is almost independent of the remnant CO white dwarf’s mass $m_{\rm c}$. Nearly all of the measured eccentricities lie below this robust theoretical limit, indicating that the eccentricity is damped during the common-envelope inspiral that follows the unstable Roche lobe overflow of the AGB star. Specifically, we focused on white dwarfs with median masses $m_{\rm c}\gt 0.6\, {\rm M}_{\odot }$. These massive white dwarfs begin their inspiral with practically identical orbital periods and eccentricities, eliminating any dependence on the initial conditions. For this sub-sample, we find an empirical relation $e\propto P^{3/2}$ between the final period and eccentricity that is much tighter than previous studies – motivating theoretical work on the eccentricity evolution during the common envelope phase. The eccentricities of lower mass CO white dwarfs may be explained by alternative formation channels.

Entanglement signature in quantum work statistics in the slow-driving regime

In slowly driven classical systems, work is a stochastic quantity and its probability distribution is known to satisfy the work fluctuation-dissipation relation, which states that the mean and variance of the dissipated work are linearly related. Recently, it was shown that generation of quantum coherence in the instantaneous energy eigenbasis leads to a correction to this linear relation in the slow-driving regime. Here, we go even further by investigating nonclassical features of work fluctuations in setups with more than one system. To do this, we first generalize slow control protocols to encompass multipartite systems, allowing for the generation of quantum correlations during the driving process. Then, focusing on two-qubit systems, we show that entanglement generation leads to a positive contribution to the dissipated work, which is distinct from the quantum correction due to local coherence generation known from previous work. Our results show that entanglement generated during slow control protocols, e.g., as an unavoidable consequence of qubit crosstalk, comes at the cost of increased dissipation. Published by the American Physical Society 2024

Coarse-Graining Conformational Dynamics with Multidimensional Generalized Langevin Equation: How, When, and Why.

A data-driven ab initio generalized Langevin equation (AIGLE) approach is developed to learn and simulate high-dimensional, heterogeneous, coarse-grained (CG) conformational dynamics. Constrained by the fluctuation-dissipation theorem, the approach can build CG models in dynamical consistency (DC) with all-atom molecular dynamics. We also propose practical criteria for AIGLE to enforce long-term DC. Case studies of a toy polymer, with 20 CG sites, and the alanine dipeptide, with two dihedral angles, elucidate why one should adopt AIGLE or its Markovian limit for modeling CG conformational dynamics in practice.

Highly efficient spectrum-splitting solar energy utilization based on near- and far-field thermophotovoltaics

Improving the efficiency of solar energy utilization systems is of great importance in solar energy utilization. Near-field thermophotovoltaic cells can achieve a high power density and, therefore, efficiently utilize radiative heat transfer. An efficient spectrum-splitting solar energy utilization system based on near- and far-field thermophotovoltaics was proposed. The input solar energy was divided by the splitter, and the two parts of the energy were utilized differently. The concentration ratio can determine the energy input of the system, which can affect the photoelectric conversion efficiency of the system. Further, the vacuum distance can modulate the near-field radiative heat transfer, thus significantly impacting system performance. Based on the fluctuation dissipation theorem and Maxwell's equations, a system model was constructed and calculated using the optimal design method, and the effects of these parameters were investigated. Moreover, the optimal efficiency was obtained under different operating conditions. The optimal cascade system efficiency reached 39.93 % at a concentration ratio of 3000, which was 15.59 % higher than that of a single photovoltaic system. Thus, this study proposes a method for the efficient utilization of solar energy. In addition, it provides guidance for the subsequent design and construction of spectrum-splitting cascade systems based on near- and far-field thermophotovoltaics.

Fluctuation-dissipation theorem and entanglement dynamics in one-dimensional low-density Jaynes-Cummings Hubbard model after a quench.

In one-dimensional low-density Jaynes-Cummings Hubbard (JCH) models [Phys. Rev. E 106, 064107 (2022)2470-004510.1103/PhysRevE.106.064107], we proved that the eigenstate thermalization hypothesis (ETH) is valid when the tunneling strength and coupling strength are of the same order. Surprisingly, at the weak tunneling limit, we observed that the entanglement entropy and scaling law of kinetic energy operators also exhibit obvious quantum chaotic properties, this is an unexpected result. To substantiate these findings, we further discuss their nonequilibrium dynamics in this paper. Our analysis reveals that when the model is a weak tunneling limit after the quench and the initial state is an equilibrium state of chaos, the system reaches an equilibrium state. This observation supports the conclusion that the low-density JCH model at the weak tunneling limit is nonintegrable, corroborating our previous results [Phys. Rev. E 106, 064107 (2022)2470-004510.1103/PhysRevE.106.064107]. Additionally, by discussing the validity of the fluctuation-dissipation theorem (FDT) and the evolution behavior of entanglement entropy and fidelity, we numerically demonstrate the differences between the one-dimensional low-density JCH model and general nonintegrable systems. Specifically, in the low-density JCH model, when the Hamiltonian after the quench is integrable, the validity of FDT depends on the thermal behavior of the initial Hamiltonian, and a metastable state is observed during the evolution of entanglement entropy. Our research presents an an intriguing and unique nonintegrable model, enriching the current understanding of nonintegrable systems.

General Relations between Stress Fluctuations and Viscoelasticity in Amorphous Polymer and Glass-Forming Systems.

Mechanical stress governs the dynamics of viscoelastic polymer systems and supercooled glass-forming fluids. It was recently established that liquids with long terminal relaxation times are characterized by transiently frozen stress fields, which, moreover, exhibit long-range correlations contributing to the dynamically heterogeneous nature of such systems. Recent studies show that stress correlations and relaxation elastic moduli are intimately related in isotropic viscoelastic systems. However, the origin of these relations (involving spatially resolved material relaxation functions) is non-trivial: some relations are based on the fluctuation-dissipation theorem (FDT), while others involve approximations. Generalizing our recent results on 2D systems, we here rigorously derive three exact FDT relations (already established in our recent investigations and, partially, in classical studies) between spatio-temporal stress correlations and generalized relaxation moduli, and a couple of new exact relations. We also derive several new approximate relations valid in the hydrodynamic regime, taking into account the effects of thermal conductivity and composition fluctuations for arbitrary space dimension. One approximate relation was heuristically obtained in our previous studies and verified using our extended simulation data on two-dimensional (2D) glass-forming systems. As a result, we provide the means to obtain, in any spatial dimension, all stress-correlation functions in terms of relaxation moduli and vice versa. The new approximate relations are tested using simulation data on 2D systems of polydisperse Lennard-Jones particles.

Probing coherent quantum thermodynamics using a trapped ion

Quantum thermodynamics is aimed at grasping thermodynamic laws as they apply to thermal machines operating in the deep quantum regime, where coherence and entanglement are expected to matter. Despite substantial progress, however, it has remained difficult to develop thermal machines in which such quantum effects are observed to be of pivotal importance. In this work, we demonstrate the possibility to experimentally measure and benchmark a genuine quantum correction, induced by quantum friction, to the classical work fluctuation-dissipation relation. This is achieved by combining laser-induced coherent Hamiltonian rotations and energy measurements on a trapped ion. Our results demonstrate that recent developments in stochastic quantum thermodynamics can be used to benchmark and unambiguously distinguish genuine quantum coherent signatures generated along driving protocols, even in presence of experimental SPAM errors and, most importantly, beyond the regimes for which theoretical predictions are available (e.g., in slow driving).

A new method to calculate broadband dielectric spectra of solvents from molecular dynamics simulations demonstrated with polarizable force fields.

Simulating the dielectric spectra of solvents requires the nuanced definition of inter- and intra-molecular forces. Non-polarizable force fields, while thoroughly benchmarked for dielectric applications, do not capture all the spectral features of solvents, such as water. Conversely, polarizable force fields have been largely untested in the context of dielectric spectroscopy but include charge and dipole fluctuations that contribute to intermolecular interactions. We benchmark non-polarizable force fields and the polarizable force fields AMOEBA03 and HIPPO for liquid water and find that the polarizable force fields can capture all the experimentally observed spectral features with varying degrees of accuracy. However, the non-polarizable force fields miss at least one peak. To diagnose this deficiency, we decompose the liquid water spectra from polarizable force fields at multiple temperatures into static and induced dipole contributions and find that the peak originates from induced dipole contributions. Broadening our inquiry to other solvents parameterized with the AMOEBA09 force field, we demonstrate good agreement between the experimental and simulated dielectric spectra of methanol and formamide. To produce these spectra, we develop a new computational approach to calculate the dielectric spectrum via the fluctuation dissipation theorem. This method minimizes the error in both the low and high frequency portions of the spectrum, improving the overall accuracy of the simulated spectrum and broadening the computed frequency range.

Reaction barriers at metal surfaces computed using the random phase approximation: Can we beat DFT in the generalized gradient approximation?

Reaction barriers for molecules dissociating on metal surfaces (as relevant to heterogeneous catalysis) are often difficult to predict accurately with density functional theory (DFT). Although the results obtained for several dissociative chemisorption reactions via DFT in the generalized gradient approximation (GGA), in meta-GGA, and for GGA exchange + van der Waals correlation scatter around the true reaction barrier, there is an entire class of dissociative chemisorption reactions for which GGA-type functionals collectively underestimate the reaction barrier. Little is known why GGA-DFT collectively fails in some cases and not in others, and we do not know whether other methods suffer from the same inconsistency. Here, we present barrier heights for dissociative chemisorption reactions obtained from the random phase approximation in the adiabatic-connection fluctuation-dissipation theorem (ACFDT-RPA) and from hybrid functionals with different amounts of exact exchange. By comparing the results obtained for the dissociative chemisorption reaction of H2 on Al(110) (where GGA-DFT collectively underestimates the barrier) and H2 on Cu(111) (where GGA-DFT scatters around the true barrier), we can gauge whether the inconsistent description of the systems persists for hybrid functionals and ACFDT-RPA. We find hybrid functionals to improve the relative description of the two systems, but to fall short of chemical accuracy. ACFDT-RPA improves the results further and leads to chemically accurate barriers for both systems. Together with an analysis of the density of states and the results from selected GGA, meta-GGA, and GGA exchange + van der Waals correlation functionals, these results allow us to discuss possible origins for the inconsistent behavior of GGA-based functionals for molecule-metal reaction barriers.

Decoherence by warm horizons

Recently Danielson, Satishchandran, and Wald (DSW) have shown that quantum superpositions held outside of Killing horizons will decohere at a steady rate. This occurs because of the inevitable radiation of soft photons (gravitons), which imprint a electromagnetic (gravitational) “which-path” memory onto the horizon. Rather than appealing to this global description, an experimenter ought to also have a local description for the cause of decoherence. One might intuitively guess that this is just the bombardment of Hawking/Unruh radiation on the system, however simple calculations challenge this idea—the same superposition held in a finite temperature inertial laboratory does not decohere at the DSW rate. In this work we provide a local description of the decoherence by mapping the DSW setup onto a worldline-localized model resembling an Unruh-DeWitt particle detector. We present an interpretation in terms of random local forces which do not sufficiently self-average over long times. Using the Rindler horizon as a concrete example we clarify the crucial role of temperature, and show that the Unruh effect is the only quantum mechanical effect underlying these random forces. A general lesson is that for an environment which induces Ohmic friction on the central system (as one gets from the classical Abraham-Lorentz-Dirac force, in an accelerating frame) the fluctuation-dissipation theorem implies that when this environment is at finite temperature it will cause steady decoherence on the central system. Our results agree with DSW and provide the complementary local perspective. Published by the American Physical Society 2024

Derivation of the nonequilibrium generalized Langevin equation from a time-dependent many-body Hamiltonian.

It has become standard practice to describe systems that remain far from equilibrium even in their steady state by Langevin equationswith colored noise which is chosen independently from the friction contribution. Since these Langevin equationsare typically not derived from first-principle Hamiltonian dynamics, it is not clear whether they correspond to physically realizable scenarios. By exact Mori projection in phase space we derive the nonequilibrium generalized Langevin equation(GLE) for an arbitrary phase-space dependent observable A from a generic many-body Hamiltonian with a time-dependent external force h(t) acting on the same observable A. This is the same Hamiltonian from which the standard fluctuation-dissipation theorem is derived, which reflects the generality of our approach. The observable A could, for example, be the position of an atom, of a molecule or of a macroscopic object, the distance between two such entities or a more complex phase-space function such as the reaction coordinate of a chemical reaction or of the folding of a protein. The Hamiltonian could, for example, describe a fluid, a solid, a viscoelastic medium, or even a turbulent inhomogeneous environment. The GLE, which is a closed-form equationof motion for the observable A, is obtained in explicit form to all orders in h(t) and without restrictions on the type of many-body Hamiltonian or the observable A. If the dynamics of the observable A corresponds to a Gaussian process, the resultant GLE has a similar form as the equilibrium Mori GLE, and in particular the friction memory kernel is given by the two-point autocorrelation function of the sum of the complementary and the external force h(t). This is a nontrivial and useful result, as many observables that characterize nonequilibrium systems display Gaussian statistics. For non-Gaussian nonequilibrium observables correction terms appear in the GLE and in the relation between the force autocorrelation and the friction memory kernel, which are explicitly given in terms of cubic correlation functions of A. Interpreting the external force h(t) as a stochastic process, we derive nonequilibrium corrections to the fluctuation-dissipation theorem and present methods to extract all GLE parameters from experimental or simulation time-series data, thus making our nonequilibrium GLE a practical tool to study and model general nonequilibrium systems.