Nonequilibrium Work Distribution Research Articles

Nonequilibrium work distributions in quantum impurity system-bath mixing processes.

The fluctuation theorem, where the central quantity is the work distribution, is an important characterization of nonequilibrium thermodynamics. In this work, based on the dissipaton-equation-of-motion theory, we develop an exact method to evaluate the work distributions in quantum impurity system-bath mixing processes in the presence of non-Markovian and strong couplings. Our results not only precisely reproduce the Jarzynski equality and Crooks relation but also reveal rich information on large deviation. The numerical demonstrations are carried out with a spin-boson model system.

Reweighted Jarzynski Sampling: Acceleration of Rare Events and Free Energy Calculation with a Bias Potential Learned from Nonequilibrium Work.

We introduce a simple enhanced sampling approach for the calculation of free energy differences and barriers along a one-dimensional reaction coordinate. First, a small number of short nonequilibrium simulations are carried out along the reaction coordinate, and the Jarzynski equality is used to learn an approximate free energy surface from the nonequilibrium work distribution. This free energy estimate is represented in a compact form as an artificial neural network and used as an external bias potential to accelerate rare events in a subsequent molecular dynamics simulation. The final free energy estimate is then obtained by reweighting the equilibrium probability distribution of the reaction coordinate sampled under the influence of the external bias. We apply our reweighted Jarzynski sampling recipe to four processes of varying scales and complexities─spanning chemical reaction in the gas phase, pair association in solution, and droplet nucleation in supersaturated vapor. In all cases, we find reweighted Jarzynski sampling to be a very efficient strategy, resulting in rapid convergence of the free energy to high precision.

Recovery of Equilibrium Free Energy from Nonequilibrium Thermodynamics with Mechanosensitive Ion Channels in E.coli.

Insitu measurements of the free energy difference between the open and closed states of ion channels are challenging due to hysteresis effects and inactivation. Exploiting recent developments in statistical physics, we present a general formalism to extract the free energy difference ΔF between the closed and open states of mechanosensitive ion channels from nonequilibrium work distributions associated with the opening and closing of the channels (gating) in response to ramp stimulation protocols recorded in native patches. We show that the work distributions obtained from the gating of MscS channels in E.coli membrane satisfy the strong symmetry relation predicted by the Crooks fluctuation theorem. Our approach enables the determination of ΔF using patch-clamp experiments, which are often inherently restricted to the nonequilibrium regime.

Lessons learned about steered molecular dynamics simulations and free energy calculations.

The calculation of free energy profiles is central in understanding differential enzymatic activity, for instance, involving chemical reactions that require QM-MM tools, ligand migration, and conformational rearrangements that can be modeled using classical potentials. The use of steered molecular dynamics (sMD) together with the Jarzynski equality is a popular approach in calculating free energy profiles. Here, we first briefly review the application of the Jarzynski equality to sMD simulations, then revisit the so-called stiff-spring approximation and the consequent expectation of Gaussian work distributions and, finally, reiterate the practical utility of the second-order cumulant expansion, as it coincides with the parametric maximum-likelihood estimator in this scenario. We illustrate this procedure using simulations of CO, both in aqueous solution and in a carbon nanotube as a model system for biologically relevant nanoheterogeneous environments. We conclude the use of the second-order cumulant expansion permits the use of faster pulling velocities in sMD simulations, without introducing bias due to large dispersion in the non-equilibrium work distribution.

Correspondence between light-absorption spectrum and nonequilibrium work distribution as a mean to access free energy differences between electronic states.

The problem of recovering the free energy difference between two electronic states has been investigated by Frezzato [Chem. Phys. Lett. 533, 106 (2012)], exploring the equivalence between light-absorption spectra and work distribution, hence opening to the application of a spectroscopic version of the Jarzynski equality (JE) [Phys. Rev. Lett. 78, 2690 (1997)]. Here, assuming the validity of the time-dependent perturbation theory, we demonstrate that such equivalence does not lead to the known form of the JE. This is ascribed to the fact that light-absorption processes cannot be described as stochastic processes. To emphasize such an aspect, we devise a stochastic model for the UV-vis (ultraviolet and visible) absorption, suitable for determining the free energy difference between two generic quantum manifolds in a JE-like fashion. However, the model would require explicit knowledge of the transition dipole moments, which are in general not available. Nonetheless, we derive a spectroscopic version of the JE that allows us to recover the free energy difference between the ground and an excited electronic state when the latter state is the only one observed in the spectrum.

Work distributions of one-dimensional fermions and bosons with dual contact interactions

We extend the well-known static duality [M. Girardeau, J. Math. Phys. 1, 516 (1960)JMAPAQ0022-248810.1063/1.1703687; T. Cheon and T. Shigehara, Phys. Rev. Lett. 82, 2536 (1999)PRLTAO0031-900710.1103/PhysRevLett.82.2536] between one-dimensional (1D) bosons and 1D fermions to the dynamical version. By utilizing this dynamical duality, we find the duality of nonequilibrium work distributions between interacting 1D bosonic (Lieb-Liniger model) and 1D fermionic (Cheon-Shigehara model) systems with dual contact interactions. As a special case, the work distribution of the Tonks-Girardeau gas is identical to that of 1D noninteracting fermionic system even though their momentum distributions are significantly different. In the classical limit, the work distributions of Lieb-Liniger models (Cheon-Shigehara models) with arbitrary coupling strength converge to that of the 1D noninteracting distinguishable particles, although their elementary excitations (quasiparticles) obey different statistics, e.g., the Bose-Einstein, the Fermi-Dirac, and the fractional statistics. We also present numerical results of the work distributions of Lieb-Liniger model with various coupling strengths, which demonstrate the convergence of work distributions in the classical limit.

Recovery of Equilibrium Free Energy from Non-Equilibrium Thermodynamics with Mechanosensitive Ion Channels in E. coli

Bacterial mechanosensitive channels are major players in cells ability to cope with hypo-osmotic stress. Excess turgor pressure due to fast water influx is reduced as the channels, triggered by membrane tension, open and release osmolytes. However, in vitro measurements of the free energy difference between the open and closed states of ion channels are challenging due to hysteresis effects and inactivation. Exploiting recent developments in statistical physics, we present a general formalism to extract the free energy difference between the closed and open states of mechanosensitive ion channels from non-equilibrium work distributions associated with the channels gating recorded in native patches under ramp stimulation protocols. We show that the work distributions obtained from the gating of MscS channels in E. coli membrane satisfy the strong symmetry relations predicted by the fluctuation theorems and recover the equilibrium free energy difference between the closed and open states of the channel within 1 k B T of its best estimate obtained from an independent experiment.

Nonequilibrium interactions between ideal polymers and a repulsive surface.

We use Newtonian and overdamped Langevin dynamics to study long flexible polymers dragged by an external force at a constant velocity v. The work W performed by that force depends on the initial state of the polymer and the details of the process. The Jarzynski equality can be used to relate the nonequilibrium work distribution P(W) obtained from repeated experiments to the equilibrium free energy difference ΔF between the initial and final states. We use the power law dependence of the geometrical and dynamical characteristics of the polymer on the number of monomers N to suggest the existence of a critical velocity v_{c}(N), such that for v<v_{c} the reconstruction of ΔF is an easy task, while for v significantly exceeding v_{c} it becomes practically impossible. We demonstrate the existence of such v_{c} analytically for an ideal polymer in free space and numerically for a polymer which is being dragged away from a repulsive wall. Our results suggest that the distribution of the dissipated work W_{d}=W-ΔF in properly scaled variables approaches a limiting shape for large N.

Work, work fluctuations, and the work distribution in a thermal nonequilibrium steady state.

Long-ranged correlations generically exist in nonequilibrium fluid systems. In the case of a nonequilibrium steady state caused by a temperature gradient, the correlations are especially long-ranged and strong. The anomalous light scattering predicted to exist in these systems is well-confirmed by numerous experiments. Recently, the Casimir force or pressure due to these fluctuations or correlations has been discussed in great detail. In this paper, the notion of a Casimir work is introduced, and an alternative way to measure the nonequilibrium Casimir force is suggested. In particular, the nonequilibrium Casimir force is related to nonequilibrium heat, and not, as in equilibrium, to a volume derivative of an average energy. The nonequilibrium work fluctuations are determined and shown to be very anomalous compared to equilibrium work fluctuations. The nonequilibrium work distribution is also computed, and it is contrasted with work distributions in systems with short-range correlations. Again, there is a striking difference in the two cases. Formal theories of work and work distributions in nonequilibrium steady states are not explicit enough to illustrate any of these interesting features.

Thermometry of ultracold atoms via nonequilibrium work distributions

Estimating the temperature of a cold quantum system is difficult. Usually, one measures a well-understood thermal state and uses that prior knowledge to infer its temperature. In contrast, we introduce a method of thermometry that assumes minimal knowledge of the state of a system and is potentially non-destructive. Our method uses a universal temperature-dependence of the quench dynamics of an initially thermal system coupled to a qubit probe that follows from the Tasaki-Crooks theorem for non-equilibrium work distributions. We provide examples for a cold-atom system, in which our thermometry protocol may retain accuracy and precision at subnanokelvin temperatures.

Statistics of work and orthogonality catastrophe in discrete level systems: an application to fullerene molecules and ultra-cold trapped Fermi gases.

The sudden introduction of a local impurity in a Fermi sea leads to an anomalous disturbance of its quantum state that represents a local quench, leaving the system out of equilibrium and giving rise to the Anderson orthogonality catastrophe. The statistics of the work done describe the energy fluctuations produced by the quench, providing an accurate and detailed insight into the fundamental physics of the process. We present here a numerical approach to the non-equilibrium work distribution, supported by applications to phenomena occurring at very diverse energy ranges. One of them is the valence electron shake-up induced by photo-ionization of a core state in a fullerene molecule. The other is the response of an ultra-cold gas of trapped fermions to an embedded two-level atom excited by a fast pulse. Working at low thermal energies, we detect the primary role played by many-particle states of the perturbed system with one or two excited fermions. We validate our approach through the comparison with some photoemission data on fullerene films and previous analytical calculations on harmonically trapped Fermi gases.

Study of Kinetic Equation for Non-Ideal Gases Using Lattice Boltzmann Method: Interparticle Forces from BBGKY Hierarchy

The first equation of the BBGKY hierarchy is closed with a truncation scheme which conserves mass, momentum and total energy. Resulting kinetic equation is solved numerically using the lattice Boltzmann method over an isothermal \(D2Q9\) lattice. The inter particle forces are derived using a density gradient approximation to the collision term of the BBGKY hierarchy and the resulting non-ideal equation of state is calculated. In this paper, we show analytically that the time rate of change of Boltzmann’s H-function i.e.,\(\frac{dH \left( t \right) }{dt}\) is zero for this truncation scheme, implying reversibility in time. Therefore, a BGK term is added to the collision integral to describe the macroscopic irreversibility. Both the local and global \(H\)-functions are calculated numerically for significant variations in the density. We also have simulated a switching experiment over this system and obtained the non-equilibrium work distributions.

Study of nonequilibrium work distributions from a fluctuating lattice Boltzmann model

A system of ideal gas is switched from an initial equilibrium state to a final state not necessarily in equilibrium, by varying a macroscopic control variable according to a well-defined protocol. The distribution of work performed during the switching process is obtained. The equilibrium free energy difference, ΔF, is determined from the work fluctuation relation. Some of the work values in the ensemble shall be less than ΔF. We term these as ones that "violate" the second law of thermodynamics. A fluctuating lattice Boltzmann model has been employed to carry out the simulation of the switching experiment. Our results show that the probability of violation of the second law increases with the increase of switching time (τ) and tends to one-half in the reversible limit of τ→∞.

Quantum and classical fluctuation theorems from a decoherent histories, open-system analysis

In this paper we present a first-principles analysis of the nonequilibrium work distribution and the free energy difference of a quantum system interacting with a general environment (with arbitrary spectral density and for all temperatures) based on a well-understood microphysics (quantum Brownian motion) model under the conditions stipulated by the Jarzynski equality [Jarzynski, Phys. Rev. Lett. 78, 2690 (1997)] and Crooks' fluctuation theorem [Crooks, Phys. Rev. E 60, 2721 (1999)] (in short, fluctuation theorems, FTs). We use the decoherent histories conceptual framework to explain how the notion of trajectories in a quantum system can be made viable and use the environment-induced decoherence scheme to assess the strength of noise that could provide sufficient decoherence to warrant the use of trajectories to define work in open quantum systems. From the solutions to the Langevin equation governing the stochastic dynamics of such systems we were able to produce formal expressions for these quantities entering in the FTs and from them prove explicitly the validity of the FTs at the high temperature limit. At low temperatures our general results would enable one to identify the range of parameters where FTs may not hold or need be expressed differently. We explain the relation between classical and quantum FTs and the advantage of this microphysics open-system approach over the phenomenological modeling and energy-level calculations for substitute closed quantum systems.

Quantum work statistics of linear and nonlinear parametric oscillators

We consider the nonequilibrium work distribution of a quantum oscillator with modulated angular frequency. We examine the discrete-to-continuous transition of the distribution as the temperature and the degree of nonadiabaticity of the frequency transformation are increased. We further develop a perturbative approach to analyze the effect of weak quartic anharmonicities, as well as of a random electric field on a charged oscillator. We find in both cases that the degree of nonadiabaticity is enhanced by the perturbation.

Employing Trapped Cold Ions to Verify the Quantum Jarzynski Equality

We propose a scheme to investigate the nonequilibrium work distribution of a quantum particle under well controlled transformations of the external potential, exploiting the versatility of a single ion in a segmented linear Paul trap. We describe in detail how the motional quantum state of a single ion can be prepared, manipulated, and finally readout to fully determine the free energy difference in both harmonic and anharmonic potentials. Uniquely to our system, we show how an ion may be immersed in an engineered laser-field reservoir. Trapped ions therefore represent an ideal tool for investigating the Jarzynski equality in open and closed quantum systems.

Approximating nonequilibrium processes using a collection of surrogate diffusion models

The surrogate process approximation (SPA) is applied to model the nonequilibrium dynamics of a reaction coordinate (RC) associated with the unfolding and refolding processes of a deca-alanine peptide at 300 K. The RC dynamics, which correspond to the evolution of the end-to-end distance of the polypeptide, are produced by steered molecular dynamics (SMD) simulations and approximated using overdamped diffusion models. We show that the collection of (estimated) SPA models contain structural information "orthogonal" to the RC monitored in this study. Functional data analysis ideas are used to correlate functions associated with the fitted SPA models with the work done on the system in SMD simulations. It is demonstrated that the shape of the nonequilibrium work distributions for the unfolding and refolding processes of deca-alanine can be predicted with functional data analysis ideas using a relatively small number of simulated SMD paths for calibrating the SPA diffusion models.

Nonequilibrium work distribution of a quantum harmonic oscillator

We calculate analytically the work distribution of a quantum harmonic oscillator with arbitrary time-dependent angular frequency. We provide detailed expressions for the work probability density for adiabatic and nonadiabatic processes, in the limits of low and high temperature. We further verify the validity of the quantum Jarzynski equality.

Nonequilibrium work distributions for a trapped Brownian particle in a time-dependent magnetic field

We study the dynamics of a trapped, charged Brownian particle in the presence of a time-dependent magnetic field. We calculate work distributions for different time-dependent protocols numerically. In our problem, thermodynamic work is related to variation of the vector potential with time as opposed to the earlier studies where the work is related to time variation of the potentials, a quantity that depends only on the coordinates of the particle. Using the Jarzynski and the Crooks equalities, we show that the free energy of the particle is independent of the magnetic field, thus complementing the Bohr-van Leeuwen theorem. We also show that our system exhibits a parametric resonance in a certain parameter space.