Controlling Uncertainty of Empirical First-Passage Times in the Small-Sample Regime.

We derive general bounds on the probability that the empirical first-passage time τ[over ¯]_{n}≡∑_{i=1}^{n}τ_{i}/n of a reversible ergodic Markov process inferred from a sample of n independent realizations deviates from the true mean first-passage time by more than any given amount in either direction. We construct nonasymptotic confidence intervals that hold in the elusive small-sample regime and thus fill the gap between asymptotic methods and the Bayesian approach that is known to be sensitive to prior belief and tends to underestimate uncertainty in the small-sample setting. We prove sharp bounds on extreme first-passage times that control uncertainty even in cases where the mean alone does not sufficiently characterize the statistics. Our concentration-of-measure-based results allow for model-free error control and reliable error estimation in kinetic inference, and are thus important for the analysis of experimental and simulation data in the presence of limited sampling.

Electrostatic pair-interaction of nearby metal or metal-coated colloids at fluid interfaces.

In this paper, we theoretically study the electrostatic interaction between a pair of identical colloids with constant surface potentials sitting in close vicinity next to each other at the fluid interface. By employing a simplified yet reasonable model system, the problem is solved within the framework of classical density functional theory and linearized as well as nonlinear Poisson-Boltzmann (PB) theory. Apart from providing a sound theoretical framework generally applicable to any such problem, our novel findings, all of which contradict common beliefs, include the following: first, quantitative and qualitative differences between the interactions obtained within the linear and the nonlinear PB theories; second, the importance of the electrostatic interaction between the omnipresent three-phase contact lines in interfacial systems; and, third, the occurrence of an attractive electrostatic interaction between a pair of identical metal colloids. The unusual attraction we report largely stems from an attractive line interaction, which although scales linearly with the size of the particle can compete with the surface interactions and can be strong enough to alter the nature of the total electrostatic interaction. Our results should find applications in metal or metal-coated particle-stabilized emulsions where densely packed particle arrays are not only frequently observed but also sometimes required.