241 research outputs found

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

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    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

    Glacial-interglacial changes in bottom-water oxygen content on the Portuguese margin

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    During the last and penultimate glacial maxima, atmospheric CO2 concentrations were lower than present, possibly in part because of increased storage of respired carbon in the deep oceans. The amount of respired carbon present in a water mass can be calculated from its oxygen content through apparent oxygen utilization; the oxygen content can in turn be calculated from the carbon isotope gradient within the sediment column. Here we analyse the shells of benthic foraminifera occurring at the sediment surface and the oxic/anoxic interface on the Portuguese Margin to reconstruct the carbon isotope gradient and hence bottom-water oxygenation over the past 150,000 years. We find that bottom-water oxygen concentrations were 45 and 65 Όmol kg−1 lower than present during the last and penultimate glacial maxima, respectively. We calculate that concentrations of remineralized organic carbon were at least twice as high as today during the glacial maxima. We attribute these changes to decreased ventilation linked to a reorganization of ocean circulation and a strengthened global biological pump. If the respired carbon pool was of a similar size throughout the entire glacial deep Atlantic basin, then this sink could account for 15 and 20 per cent of the glacial PCO2 drawdown during the last and penultimate glacial maxima

    Engineered swift equilibration of a Brownian particle

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    A fundamental and intrinsic property of any device or natural system is its relaxation time relax, which is the time it takes to return to equilibrium after the sudden change of a control parameter [1]. Reducing tautau relax , is frequently necessary, and is often obtained by a complex feedback process. To overcome the limitations of such an approach, alternative methods based on driving have been recently demonstrated [2, 3], for isolated quantum and classical systems [4--9]. Their extension to open systems in contact with a thermostat is a stumbling block for applications. Here, we design a protocol,named Engineered Swift Equilibration (ESE), that shortcuts time-consuming relaxations, and we apply it to a Brownian particle trapped in an optical potential whose properties can be controlled in time. We implement the process experimentally, showing that it allows the system to reach equilibrium times faster than the natural equilibration rate. We also estimate the increase of the dissipated energy needed to get such a time reduction. The method paves the way for applications in micro and nano devices, where the reduction of operation time represents as substantial a challenge as miniaturization [10]. The concepts of equilibrium and of transformations from an equilibrium state to another, are cornerstones of thermodynamics. A textbook illustration is provided by the expansion of a gas, starting at equilibrium and expanding to reach a new equilibrium in a larger vessel. This operation can be performed either very slowly by a piston, without dissipating energy into the environment, or alternatively quickly, letting the piston freely move to reach the new volume

    Antiepileptic Drugs and Suicide: A Systematic Review of Adverse Effects

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    &lt;b&gt;&lt;i&gt;Background:&lt;/i&gt;&lt;/b&gt; Since the FDA (Food and Drug Administration) report on antiepileptic drugs (AEDs) and suicide risk was released (2008), several studies have been published on this controversial relationship. This systematic review (SR) gives an updated approach to this health issue. &lt;b&gt;&lt;i&gt;Summary:&lt;/i&gt;&lt;/b&gt; We searched 6 databases. We ultimately included 11 publications: 4 cohort studies, 1 case-crossover study, 2 community case-control studies, and 4 SRs. Overall, 1 SR described studies already included; 3 studies reported a 2- to 4-fold overall increase in risk; 1 study reported an increased risk of suicide among epilepsy patients on AEDs with high risk of depression; 1study showed a protective effect among epilepsy patients; 2 studies were conducted with patients with bipolar disorder (1 showed a protective effect, whereas the other showed a 3-fold increase in risk of suicide), and the other 3 studies reported results for single AEDs. Several biases affected the published results. &lt;b&gt;&lt;i&gt;Key Messages:&lt;/i&gt;&lt;/b&gt; There is no clear evidence of an association between the use of AEDs and an increased risk of suicide because of the heterogeneity in the studies at the clinical and methodological level. A future study should cover all indications for use, retrieve information from a healthcare database, and include a defined set of covariates to avoid bias.</jats:p

    Efficiency of Free Energy Transduction in Autonomous Systems

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    We consider the thermodynamics of chemical coupling from the viewpoint of free energy transduction efficiency. In contrast to an external parameter-driven stochastic energetics setup, the dynamic change of the equilibrium distribution induced by chemical coupling, adopted, for example, in biological systems, is inevitably an autonomous process. We found that the efficiency is bounded by the ratio between the non-symmetric and the symmetrized Kullback-Leibler distance, which is significantly lower than unity. Consequences of this low efficiency are demonstrated in the simple two-state case, which serves as an important minimal model for studying the energetics of biomolecules.Comment: 4 pages, 4 figure

    Energetics and performance of a microscopic heat engine based on exact calculations of work and heat distributions

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    We investigate a microscopic motor based on an externally controlled two-level system. One cycle of the motor operation consists of two strokes. Within each stroke, the two-level system is in contact with a given thermal bath and its energy levels are driven with a constant rate. The time evolution of the occupation probabilities of the two states are controlled by one rate equation and represent the system's response with respect to the external driving. We give the exact solution of the rate equation for the limit cycle and discuss the emerging thermodynamics: the work done on the environment, the heat exchanged with the baths, the entropy production, the motor's efficiency, and the power output. Furthermore we introduce an augmented stochastic process which reflects, at a given time, both the occupation probabilities for the two states and the time spent in the individual states during the previous evolution. The exact calculation of the evolution operator for the augmented process allows us to discuss in detail the probability density for the performed work during the limit cycle. In the strongly irreversible regime, the density exhibits important qualitative differences with respect to the more common Gaussian shape in the regime of weak irreversibility.Comment: 21 pages, 7 figure

    Optimal protocols for Hamiltonian and Schr\"odinger dynamics

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    For systems in an externally controllable time-dependent potential, the optimal protocol minimizes the mean work spent in a finite-time transition between given initial and final values of a control parameter. For an initially thermalized ensemble, we consider both Hamiltonian evolution for classical systems and Schr\"odinger evolution for quantum systems. In both cases, we show that for harmonic potentials, the optimal work is given by the adiabatic work even in the limit of short transition times. This result is counter-intuitive because the adiabatic work is substantially smaller than the work for an instantaneous jump. We also perform numerical calculations of the optimal protocol for Hamiltonian dynamics in an anharmonic quartic potential. For a two-level spin system, we give examples where the adiabatic work can be reached in either a finite or an arbitrarily short transition time depending on the allowed parameter space.Comment: submitted to J. Stat. Mech.: Theor. Exp

    Ultrathin 2 nm gold as ideal impedance-matched absorber for infrared light

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    Thermal detectors are a cornerstone of infrared (IR) and terahertz (THz) technology due to their broad spectral range. These detectors call for suitable broad spectral absorbers with minimalthermal mass. Often this is realized by plasmonic absorbers, which ensure a high absorptivity butonly for a narrow spectral band. Alternativly, a common approach is based on impedance-matching the sheet resistance of a thin metallic film to half the free-space impedance. Thereby, it is possible to achieve a wavelength-independent absorptivity of up to 50 %, depending on the dielectric properties of the underlying substrate. However, existing absorber films typicallyrequire a thickness of the order of tens of nanometers, such as titanium nitride (14 nm), whichcan significantly deteriorate the response of a thermal transducers. Here, we present the application of ultrathin gold (2 nm) on top of a 1.2 nm copper oxide seed layer as an effective IR absorber. An almost wavelength-independent and long-time stable absorptivity of 47(3) %, ranging from 2 Ό\mum to 20 Ό\mum, could be obtained and is further discussed. The presented gold thin-film represents analmost ideal impedance-matched IR absorber that allows a significant improvement of state-of-the-art thermal detector technology

    Heat release by controlled continuous-time Markov jump processes

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    We derive the equations governing the protocols minimizing the heat released by a continuous-time Markov jump process on a one-dimensional countable state space during a transition between assigned initial and final probability distributions in a finite time horizon. In particular, we identify the hypotheses on the transition rates under which the optimal control strategy and the probability distribution of the Markov jump problem obey a system of differential equations of Hamilton-Bellman-Jacobi-type. As the state-space mesh tends to zero, these equations converge to those satisfied by the diffusion process minimizing the heat released in the Langevin formulation of the same problem. We also show that in full analogy with the continuum case, heat minimization is equivalent to entropy production minimization. Thus, our results may be interpreted as a refined version of the second law of thermodynamics.Comment: final version, section 2.1 revised, 26 pages, 3 figure
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