Itay Barel

Probing static disorder in Arrhenius kinetics by single-molecule force spectroscopy

The widely used Arrhenius equation describes the kinetics of simple two-state reactions, with the implicit assumption of a single transition state with a well-defined activation energy barrier ΔE, as the rate-limiting step. However, it has become increasingly clear that the saddle point of the free-energy surface in most reactions is populated by ensembles of conformations, leading to nonexponential kinetics. Here we present a theory that generalizes the Arrhenius equation to include static disorder of conformational degrees of freedom as a function of an external perturbation to fully account for a diverse set of transition states. The effect of a perturbation on static disorder is best examined at the single-molecule level. Here we use force-clamp spectroscopy to study the nonexponential kinetics of single ubiquitin proteins unfolding under force. We find that the measured variance in ΔE shows both force-dependent and independent components, where the force-dependent component scales with F2, in excellent agreement with our theory. Our study illustrates a novel adaptation of the classical Arrhenius equation that accounts for the microscopic origins of nonexponential kinetics, which are essential in understanding the rapidly growing body of single-molecule data.

Friction on a Microstructured Elastomer Surface

The friction of microstructured polydimethylsiloxane samples against a glass surface is studied through force measurements and simultaneous optical microscopy. Both average friction forces and the amplitude of stick-slip oscillations are greatly reduced by the structuring. Optical microscopy reveals waves propagating through the contact in connection which stick-slip events. The experimental observations are interpreted with the help of simulations of a spring-block model for which parameters are directly derived from the experiment. Stress gradients across the contact area are found to play an important role for the frictional behavior.

Stabilizing stick-slip friction

Even the most regular stick-slip frictional sliding is always stochastic, with irregularity in both the intervals between slip events and the sizes of the associated stress drops. Applying small-amplitude oscillations to the shear force, we show, experimentally and theoretically, that the stick-slip periods synchronize. We further show that this phase locking is related to the inhibition of slow rupture modes which forces a transition to fast rupture, providing a possible mechanism for observed remote triggering of earthquakes. Such manipulation of collective modes may be generally relevant to extended nonlinear systems driven near to criticality.

Probing and tuning frictional aging at the nanoscale

Time-dependent increase of frictional strength, or frictional aging, is a widely observed phenomenon both at macro and nanoscales. The frictional aging at the nanoscale may result from nucleation of capillary bridges and strengthening of chemical bonding, and it imposes serious constraints and limitations on the performance and lifetime of micro- and nanomachines. Here, by analytical model and numerical simulations, we investigate the effect of inplane oscillations on friction in nanoscale contacts which exhibit aging. We demonstrate that adding a low amplitude oscillatory component to the pulling force, when applied at the right frequency, can significantly suppress aging processes and thereby reduce friction. The results obtained show that frictional measurements performed in this mode can provide significant information on the mechanism of frictional aging and stiffness of interfacial contacts.

Friction through reversible jumps of surface atoms.

We propose a microscopic model that incorporates the effect of thermally activated motion of surface atoms on nanoscopic friction. Our calculations demonstrate that the stick-slip motion of the tip is governed by two competing processes: (i) jumps of the surface atoms to the tip which tend to inhibit sliding, and (ii) jumps back to the sample which give rise to sliding. The energy dissipated during the reversible jumps of the surface atoms between the sample and tip contributes significantly to the friction force, and leads to a nonmonotonic dependence of friction on temperature, which has been observed in recent friction force microscopy experiments for different material classes. The proposed model elucidates the physical origin of microscopic instabilities introduced in phenomenological models for the interpretation of the experimental results.