TY - JOUR A1 - Godec, Aljaz A1 - Metzler, Ralf T1 - Universal Proximity Effect in Target Search Kinetics in the Few-Encounter Limit JF - Physical review : X, Expanding access N2 - When does a diffusing particle reach its target for the first time? This first-passage time (FPT) problem is central to the kinetics of molecular reactions in chemistry and molecular biology. Here, we explain the behavior of smooth FPT densities, for which all moments are finite, and demonstrate universal yet generally non-Poissonian long-time asymptotics for a broad variety of transport processes. While Poisson-like asymptotics arise generically in the presence of an effective repulsion in the immediate vicinity of the target, a time-scale separation between direct and reflected indirect trajectories gives rise to a universal proximity effect: Direct paths, heading more or less straight from the point of release to the target, become typical and focused, with a narrow spread of the corresponding first-passage times. Conversely, statistically dominant indirect paths exploring the entire system tend to be massively dissimilar. The initial distance to the target particularly impacts gene regulatory or competitive stochastic processes, for which few binding events often determine the regulatory outcome. The proximity effect is independent of details of the transport, highlighting the robust character of the FPT features uncovered here. Y1 - 2016 U6 - https://doi.org/10.1103/PhysRevX.6.041037 SN - 2160-3308 VL - 6 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Godec, Aljaz A1 - Smith, Jeremy C. A1 - Merzel, Franci T1 - Soft Collective Fluctuations Governing Hydrophobic Association JF - PHYSICAL REVIEW LETTERS N2 - The interaction between two associating hydrophobic particles has traditionally been explained in terms of the release of entropically frustrated hydration shell water molecules. However, this picture cannot account for the kinetics of hydrophobic association and is therefore not capable of providing a microscopic description of the hydrophobic interaction (HI). Here, Monte Carlo simulations of a pair of molecular-scale apolar solutes in aqueous solution reveal the critical role of collective fluctuations in the hydrogen bond (HB) network for the microscopic picture of the HI. The main contribution to the HI is the relaxation of solute-water translational correlations. The existence of a heat capacity maximum at the desolvation barrier is shown to arise from softening of non-HB water fluctuations and the relaxation of many-body correlations in the labile HB network. The microscopic event governing the kinetics of hydrophobic association has turned out to be a relatively large critical collective fluctuation in hydration water displacing a substantial fraction of HB clusters from the inner to the outer region of the first hydration shell. Y1 - 2013 U6 - https://doi.org/10.1103/PhysRevLett.111.127801 SN - 0031-9007 VL - 111 IS - 12 PB - AMER PHYSICAL SOC CY - COLLEGE PK ER - TY - JOUR A1 - Schwarzl, Maria A1 - Godec, Aljaz A1 - Metzler, Ralf T1 - Quantifying non-ergodicity of anomalous diffusion with higher order moments JF - Scientific reports N2 - Anomalous diffusion is being discovered in a fast growing number of systems. The exact nature of this anomalous diffusion provides important information on the physical laws governing the studied system. One of the central properties analysed for finite particle motion time series is the intrinsic variability of the apparent diffusivity, typically quantified by the ergodicity breaking parameter EB. Here we demonstrate that frequently EB is insufficient to provide a meaningful measure for the observed variability of the data. Instead, important additional information is provided by the higher order moments entering by the skewness and kurtosis. We analyse these quantities for three popular anomalous diffusion models. In particular, we find that even for the Gaussian fractional Brownian motion a significant skewness in the results of physical measurements occurs and needs to be taken into account. Interestingly, the kurtosis and skewness may also provide sensitive estimates of the anomalous diffusion exponent underlying the data. We also derive a new result for the EB parameter of fractional Brownian motion valid for the whole range of the anomalous diffusion parameter. Our results are important for the analysis of anomalous diffusion but also provide new insights into the theory of anomalous stochastic processes. Y1 - 2017 U6 - https://doi.org/10.1038/s41598-017-03712-x SN - 2045-2322 VL - 7 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Godec, Aljaz A1 - Metzler, Ralf T1 - Optimization and universality of Brownian search in a basic model of quenched heterogeneous media JF - Physical review : E, Statistical, nonlinear and soft matter physics N2 - The kinetics of a variety of transport-controlled processes can be reduced to the problem of determining the mean time needed to arrive at a given location for the first time, the so-called mean first-passage time ( MFPT) problem. The occurrence of occasional large jumps or intermittent patterns combining various types of motion are known to outperform the standard random walk with respect to the MFPT, by reducing oversampling of space. Here we show that a regular but spatially heterogeneous random walk can significantly and universally enhance the search in any spatial dimension. In a generic minimal model we consider a spherically symmetric system comprising two concentric regions with piecewise constant diffusivity. The MFPT is analyzed under the constraint of conserved average dynamics, that is, the spatially averaged diffusivity is kept constant. Our analytical calculations and extensive numerical simulations demonstrate the existence of an optimal heterogeneity minimizing the MFPT to the target. We prove that the MFPT for a random walk is completely dominated by what we term direct trajectories towards the target and reveal a remarkable universality of the spatially heterogeneous search with respect to target size and system dimensionality. In contrast to intermittent strategies, which are most profitable in low spatial dimensions, the spatially inhomogeneous search performs best in higher dimensions. Discussing our results alongside recent experiments on single-particle tracking in living cells, we argue that the observed spatial heterogeneity may be beneficial for cellular signaling processes. Y1 - 2015 U6 - https://doi.org/10.1103/PhysRevE.91.052134 SN - 1539-3755 SN - 1550-2376 VL - 91 IS - 5 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Godec, Aljaz A1 - Chechkin, Aleksei V. A1 - Barkai, Eli A1 - Kantz, Holger A1 - Metzler, Ralf T1 - Localisation and universal fluctuations in ultraslow diffusion processes JF - Journal of physics : A, Mathematical and theoretical N2 - We study ultraslow diffusion processes with logarithmic mean squared displacement (MSD) < x(2)(t)> similar or equal to log(gamma)t. Comparison of annealed (renewal) continuous time random walks (CTRWs) with logarithmic waiting time distribution psi(tau) similar or equal to 1/(tau log(1+gamma)tau) and Sinai diffusion in quenched random landscapes reveals striking similarities, despite the great differences in their physical nature. In particular, they exhibit a weakly non-ergodic disparity of the time-averaged and ensemble-averaged MSDs. Remarkably, for the CTRW we observe that the fluctuations of time averages become universal, with an exponential suppression of mobile trajectories. We discuss the fundamental connection between the Golosov localization effect and non-ergodicity in the sense of the disparity between ensemble-averaged MSD and time-averaged MSD. KW - Sinai diffusion KW - anomalous diffusion KW - quenched energy landscape Y1 - 2014 U6 - https://doi.org/10.1088/1751-8113/47/49/492002 SN - 1751-8113 SN - 1751-8121 VL - 47 IS - 49 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Krüsemann, Henning A1 - Godec, Aljaz A1 - Metzler, Ralf T1 - First-passage statistics for aging diffusion in systems with annealed and quenched disorder JF - Physical review : E, Statistical, nonlinear and soft matter physics N2 - Aging, the dependence of the dynamics of a physical process on the time t(a) since its original preparation, is observed in systems ranging from the motion of charge carriers in amorphous semiconductors over the blinking dynamics of quantum dots to the tracer dispersion in living biological cells. Here we study the effects of aging on one of the most fundamental properties of a stochastic process, the first-passage dynamics. We find that for an aging continuous time random walk process, the scaling exponent of the density of first-passage times changes twice as the aging progresses and reveals an intermediate scaling regime. The first-passage dynamics depends on t(a) differently for intermediate and strong aging. Similar crossovers are obtained for the first-passage dynamics for a confined and driven particle. Comparison to the motion of an aged particle in the quenched trap model with a bias shows excellent agreement with our analytical findings. Our results demonstrate how first-passage measurements can be used to unravel the age t(a) of a physical system. Y1 - 2014 U6 - https://doi.org/10.1103/PhysRevE.89.040101 SN - 1539-3755 SN - 1550-2376 VL - 89 IS - 4 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Godec, Aljaz A1 - Metzler, Ralf T1 - First passage time distribution in heterogeneity controlled kinetics: going beyond the mean first passage time JF - Scientific reports N2 - The first passage is a generic concept for quantifying when a random quantity such as the position of a diffusing molecule or the value of a stock crosses a preset threshold (target) for the first time. The last decade saw an enlightening series of new results focusing mostly on the so-called mean and global first passage time (MFPT and GFPT, respectively) of such processes. Here we push the understanding of first passage processes one step further. For a simple heterogeneous system we derive rigorously the complete distribution of first passage times (FPTs). Our results demonstrate that the typical FPT significantly differs from the MFPT, which corresponds to the long time behaviour of the FPT distribution. Conversely, the short time behaviour is shown to correspond to trajectories connecting directly from the initial value to the target. Remarkably, we reveal a previously overlooked third characteristic time scale of the first passage dynamics mirroring brief excursion away from the target. Y1 - 2016 U6 - https://doi.org/10.1038/srep20349 SN - 2045-2322 VL - 6 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Godec, Aljaz A1 - Metzler, Ralf T1 - Finite-Time effects and ultraweak ergodicity breaking in superdiffusive dynamics JF - Physical review letters N2 - We study the ergodic properties of superdiffusive, spatiotemporally coupled Levy walk processes. For trajectories of finite duration, we reveal a distinct scatter of the scaling exponents of the time averaged mean squared displacement (delta x(2)) over bar around the ensemble value 3 - alpha (1 < alpha < 2) ranging from ballistic motion to subdiffusion, in strong contrast to the behavior of subdiffusive processes. In addition we find a significant dependence of the average of (delta x(2)) over bar over an ensemble of trajectories as a function of the finite measurement time. This so-called finite-time amplitude depression and the scatter of the scaling exponent is vital in the quantitative evaluation of superdiffusive processes. Comparing the long time average of the second moment with the ensemble mean squared displacement, these only differ by a constant factor, an ultraweak ergodicity breaking. Y1 - 2013 U6 - https://doi.org/10.1103/PhysRevLett.110.020603 SN - 0031-9007 VL - 110 IS - 2 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Bauer, Maximilian A1 - Godec, Aljaz A1 - Metzler, Ralf T1 - Diffusion of finite-size particles in two-dimensional channels with random wall configurations JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - Diffusion of chemicals or tracer molecules through complex systems containing irregularly shaped channels is important in many applications. Most theoretical studies based on the famed Fick-Jacobs equation focus on the idealised case of infinitely small particles and reflecting boundaries. In this study we use numerical simulations to consider the transport of finite-size particles through asymmetrical two-dimensional channels. Additionally, we examine transient binding of the molecules to the channel walls by applying sticky boundary conditions. We consider an ensemble of particles diffusing in independent channels, which are characterised by common structural parameters. We compare our results for the long-time effective diffusion coefficient with a recent theoretical formula obtained by Dagdug and Pineda Y1 - 2014 U6 - https://doi.org/10.1039/c3cp55160a SN - 1463-9076 SN - 1463-9084 VL - 16 IS - 13 SP - 6118 EP - 6128 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Godec, Aljaz A1 - Bauer, Maximilian A1 - Metzler, Ralf T1 - Collective dynamics effect transient subdiffusion of inert tracers in flexible gel networks JF - New journal of physics : the open-access journal for physics N2 - Based on extensive Brownian dynamics simulations we study the thermal motion of a tracer bead in a cross-linked, flexible gel in the limit when the tracer particle size is comparable to or even larger than the equilibrium mesh size of the gel. The analysis of long individual trajectories of the tracer demonstrates the existence of pronounced transient anomalous diffusion. From the time averaged mean squared displacement and the time averaged van Hove correlation functions we elucidate the many-body origin of the non-Brownian tracer bead dynamics. Our results shed new light onto the ongoing debate over the physical origin of steric tracer interactions with structured environments. KW - anomalous diffusion KW - gel network KW - van Hove correlation Y1 - 2014 U6 - https://doi.org/10.1088/1367-2630/16/9/092002 SN - 1367-2630 VL - 16 PB - IOP Publ. Ltd. CY - Bristol ER -