arXiv subjects

Gavin E. Crooks

Publications and source records attributed to Gavin E. Crooks.

34 records · Page 2Linked to original sources

arXiv2012

Thermodynamic metrics and optimal paths

A fundamental problem in modern thermodynamics is how a molecular-scale machine performs useful work, while operating away from thermal equilibrium without excessive dissipation. To this end, we derive a friction tensor that induces a Riemannian manifold on the space of thermodynamic states. Within the linear-response regime, this metric structure controls the dissipation of finite-time transformations, and bestows optimal protocols with many useful properties. We discuss the connection to the existing thermodynamic length formalism, and demonstrate the utility of this metric by solving for optimal control parameter protocols in a simple nonequilibrium model.

cond-mat.stat-mech↗

arXiv2012

Near-equilibrium measurements of nonequilibrium free energy

A central endeavor of thermodynamics is the measurement of free energy changes. Regrettably, although we can measure the free energy of a system in thermodynamic equilibrium, typically all we can say about the free energy of a non-equilibrium ensemble is that it is larger than that of the same system at equilibrium. Herein, we derive a formally exact expression for the probability distribution of a driven system, which involves path ensemble averages of the work over trajectories of the time-reversed system. From this we find a simple near-equilibrium approximation for the free energy in terms of an excess mean time-reversed work, which can be experimentally measured on real systems. With analysis and computer simulation, we demonstrate the accuracy of our approximations for several simple models.

cond-mat.stat-mech↗

arXiv2011

Nonequilibrium candidate Monte Carlo: A new tool for efficient equilibrium simulation

Metropolis Monte Carlo simulation is a powerful tool for studying the equilibrium properties of matter. In complex condensed-phase systems, however, it is difficult to design Monte Carlo moves with high acceptance probabilities that also rapidly sample uncorrelated configurations. Here, we introduce a new class of moves based on nonequilibrium dynamics: candidate configurations are generated through a finite-time process in which a system is actively driven out of equilibrium, and accepted with criteria that preserve the equilibrium distribution. The acceptance rule is similar to the Metropolis acceptance probability, but related to the nonequilibrium work rather than the instantaneous energy difference. Our method is applicable to sampling from both a single thermodynamic state or a mixture of thermodynamic states, and allows both coordinates and thermodynamic parameters to be driven in nonequilibrium proposals. While generating finite-time switching trajectories incurs an additional cost, driving some degrees of freedom while allowing others to evolve naturally can lead to large enhancements in acceptance probabilities, greatly reducing structural correlation times. Using nonequilibrium driven processes vastly expands the repertoire of useful Monte Carlo proposals in simulations of dense solvated systems.

cond-mat.stat-mech↗

arXiv2008

The length of time's arrow

An unresolved problem in physics is how the thermodynamic arrow of time arises from an underlying time reversible dynamics. We contribute to this issue by developing a measure of time-symmetry breaking, and by using the work fluctuation relations, we determine the time asymmetry of recent single molecule RNA unfolding experiments. We define time asymmetry as the Jensen-Shannon divergence between trajectory probability distributions of an experiment and its time-reversed conjugate. Among other interesting properties, the length of time's arrow bounds the average dissipation and determines the difficulty of accurately estimating free energy differences in nonequilibrium experiments.

cond-mat.stat-mech↗

arXiv2008

Far-from-Equilibrium Measurements of Thermodynamic Length

Thermodynamic length is a path function that generalizes the notion of length to the surface of thermodynamic states. Here, we show how to measure thermodynamic length in far-from-equilibrium single molecule experiments using the work fluctuation relations. For these microscopic systems, it proves necessary to define the thermodynamic length in terms of the Fisher information. Consequently, the thermodynamic length can be directly related to the magnitude of fluctuations about equilibrium. The work fluctuation relations link the work and the free energy change during an external perturbation on a system. We use this result to determine equilibrium averages at intermediate points of the protocol in which the system is out-of-equilibrium. This allows us to extend Bennett's method to determine the potential of mean force, as well as the thermodynamic length, in single molecule experiments.

cond-mat.stat-mech↗

arXiv2007

Measuring thermodynamic length

Thermodynamic length is a metric distance between equilibrium thermodynamic states. Among other interesting properties, this metric asymptotically bounds the dissipation induced by a finite time transformation of a thermodynamic system. It is also connected to the Jensen-Shannon divergence, Fisher information and Rao's entropy differential metric. Therefore, thermodynamic length is of central interest in understanding matter out-of-equilibrium. In this paper, we will consider how to define thermodynamic length for a small system described by equilibrium statistical mechanics and how to measure thermodynamic length within a computer simulation. Surprisingly, Bennett's classic acceptance ratio method for measuring free energy differences also measures thermodynamic length.

cond-mat.stat-mech↗

arXiv2007

Bayesian estimates of free energies from nonequilibrium work data in the presence of instrument noise

The Jarzynski equality and the fluctuation theorem relate equilibrium free energy differences to non-equilibrium measurements of the work. These relations extend to single-molecule experiments that have probed the finite-time thermodynamics of proteins and nucleic acids. The effects of experimental error and instrument noise have not previously been considered. Here, we present a Bayesian formalism for estimating free-energy changes from non-equilibrium work measurements that compensates for instrument noise and combines data from multiple driving protocols. We reanalyze a recent set of experiments in which a single RNA hairpin is unfolded and refolded using optical tweezers at three different rates. Interestingly, the fastest and farthest-from-equilibrium measurements contain the least instrumental noise, and therefore provide a more accurate estimate of the free energies than a few slow, more noisy, near-equilibrium measurements. The methods we propose here will extend the scope of single-molecule experiments; they can be used in the analysis of data from measurements with AFM, optical, and magnetic tweezers.

cond-mat.stat-mech↗

arXiv2007

Quantum Operation Time Reversal

The dynamics of an open quantum system can be described by a quantum operation, a linear, complete positive map of operators. Here, I exhibit a compact expression for the time reversal of a quantum operation, which is closely analogous to the time reversal of a classical Markov transition matrix. Since open quantum dynamics are stochastic, and not, in general, deterministic, the time reversal is not, in general, an inversion of the dynamics. Rather, the system relaxes towards equilibrium in both the forward and reverse time directions. The probability of a quantum trajectory and the conjugate, time reversed trajectory are related by the heat exchanged with the environment.

quant-ph↗

arXiv2007

On the Quantum Jarzynski Identity

In this note, we will discuss how to compactly express and prove the Jarzynski identity for an open quantum system with dissipative dynamics. We will avoid explicitly measuring the work directly, which is tantamount to continuously monitoring the system, and instead measure the heat flow from the environment. We represent the measurement of heat flow with Hermitian map superoperators that act on the system density matrix. Hermitian maps provide a convenient and compact representation of sequential measurement and correlation functions.

cond-mat.stat-mech↗

arXiv2006

On the work distribution for the adiabatic compression of a dilute classical gas

We consider the adiabatic and quasi-static compression of a dilute classical gas, confined in a piston and initially equilibrated with a heat bath. We find that the work performed during this process is described statistically by a gamma distribution. We use this result to show that the model satisfies the non-equilibrium work and fluctuation theorems, but not the flucutation-dissipation relation. We discuss the rare but dominant realizations that contribute most to the exponential average of the work, and relate our results to potentially universal work distributions.

cond-mat.stat-mech↗

arXiv2006

Beyond Boltzmann-Gibbs statistics: Maximum entropy hyperensembles out-of-equilibrium

What is the best description that we can construct of a thermodynamic system that is not in equilibrium, given only one, or a few, extra parameters over and above those needed for a description of the same system at equilibrium? Here, we argue the most appropriate additional parameter is the non-equilibrium entropy of the system, and that we should not attempt to estimate the probability distribution of the system, but rather the metaprobability (or hyperensemble) that the system is described by a particular probability distribution. The result is an entropic distribution with two parameters, one a non-equilibrium temperature, and the other a measure of distance from equilibrium. This dispersion parameter smoothly interpolates between certainty of a canonical distribution at equilibrium and great uncertainty as to the probability distribution as we move away from equilibrium. We deduce that, in general, large, rare fluctuations become far more common as we move away from equilibrium.

cond-mat.stat-mech↗

arXiv2005

Pairwise alignment incorporating dipeptide covariation

Motivation: Standard algorithms for pairwise protein sequence alignment make the simplifying assumption that amino acid substitutions at neighboring sites are uncorrelated. This assumption allows implementation of fast algorithms for pairwise sequence alignment, but it ignores information that could conceivably increase the power of remote homolog detection. We examine the validity of this assumption by constructing extended substitution matrixes that encapsulate the observed correlations between neighboring sites, by developing an efficient and rigorous algorithm for pairwise protein sequence alignment that incorporates these local substitution correlations, and by assessing the ability of this algorithm to detect remote homologies. Results: Our analysis indicates that local correlations between substitutions are not strong on the average. Furthermore, incorporating local substitution correlations into pairwise alignment did not lead to a statistically significant improvement in remote homology detection. Therefore, the standard assumption that individual residues within protein sequences evolve independently of neighboring positions appears to be an efficient and appropriate approximation.

q-bio.BM↗

arXiv2004

An Alternative Model of Amino Acid Replacement

The observed correlations between pairs of homologous protein sequences are typically explained in terms of a Markovian dynamic of amino acid substitution. This model assumes that every location on the protein sequence has the same background distribution of amino acids, an assumption that is incompatible with the observed heterogeneity of protein amino acid profiles and with the success of profile multiple sequence alignment. We propose an alternative model of amino acid replacement during protein evolution based upon the assumption that the variation of the amino acid background distribution from one residue to the next is sufficient to explain the observed sequence correlations of homologs. The resulting dynamical model of independent replacements drawn from heterogeneous backgrounds is simple and consistent, and provides a unified homology match score for sequence-sequence, sequence-profile and profile-profile alignment.

q-bio.BM↗

arXiv2003

Protein secondary structure: Entropy, correlations and prediction

Is protein secondary structure primarily determined by local interactions between residues closely spaced along the amino acid backbone, or by non-local tertiary interactions? To answer this question we have measured the entropy densities of primary structure and secondary structure sequences, and the local inter-sequence mutual information density. We find that the important inter-sequence interactions are short ranged, that correlations between neighboring amino acids are essentially uninformative, and that only 1/4 of the total information needed to determine the secondary structure is available from local inter-sequence correlations. Since the remaining information must come from non-local interactions, this observation supports the view that the majority of most proteins fold via a cooperative process where secondary and tertiary structure form concurrently. To provide a more direct comparison to existing secondary structure prediction methods, we construct a simple hidden Markov model (HMM) of the sequences. This HMM achieves a prediction accuracy comparable to other single sequence secondary structure prediction algorithms, and can extract almost all of the inter-sequence mutual information. This suggests that these algorithms are almost optimal, and that we should not expect a dramatic improvement in prediction accuracy. However, local correlations between secondary and primary structure are probably of under-appreciated importance in many tertiary structure prediction methods, such as threading.

q-bio.BM↗

arXiv1999

Path ensembles averages in systems driven far-from-equilibrium

The Kawasaki nonlinear response relation, the transient fluctuation theorem, and the Jarzynski nonequilibrium work relation are all expressions that describe the behavior of a system that has been driven from equilibrium by an external perturbation. In contrast to linear response theory, these expressions are exact no matter the strength of the perturbation, or how far the system has been driven away from equilibrium. In this paper I show that these three relations (and several other closely related results) can all be considered special cases of a single theorem. This expression is explicitly derived for discrete time and space Markovian dynamics, with the additional assumptions that the single time step dynamics preserve the appropriate equilibrium ensemble, and that the energy of the system remains finite.

cond-mat.stat-mech↗

arXiv1999

The Entropy Production Fluctuation Theorem and the Nonequilibrium Work Relation for Free Energy Differences

There are only a very few known relations in statistical dynamics that are valid for systems driven arbitrarily far-from-equilibrium. One of these is the fluctuation theorem, which places conditions on the entropy production probability distribution of nonequilibrium systems. Another recently discovered far-from-equilibrium expression relates nonequilibrium measurements of the work done on a system to equilibrium free energy differences. In this paper, we derive a generalized version of the fluctuation theorem for stochastic, microscopically reversible dynamics. Invoking this generalized theorem provides a succinct proof of the nonequilibrium work relation.

cond-mat.stat-mech↗