Non-Markov bond model for dynamic force spectroscopy

Single-molecule force spectroscopy data are conventionally analyzed using a schematic model, wherein a molecular bond is represented as a virtual particle diffusing in a one-dimensional free-energy landscape. However, this simple and efficient approach is unable to account for the "anomalous" bond-breaking kinetics increasingly observed in force spectroscopy experiments and simulations, e.g., in the form of non-exponential distributions of bond lifetimes under constant load. Here, we show that such characteristic traits arise naturally in a rigorous extension of the one-dimensional theory that accounts for the transient dynamics of a generic set of coupled degrees of freedom. These "hidden modes" affect the reaction dynamics in various ways, depending on their relaxation spectrum and the loading protocol, giving rise, in particular, to apparent static and dynamic disorder. In two complementary asymptotic limits, we are able to find exact analytical expressions for pertinent experimental observables, such as the mean rupture force and the rupture-force distribution. Intriguingly, our asymptotic results become unconditionally exact at high loading rates, thus providing us with a microscopically consistent theory of rapid force spectroscopy that avoids the usual Markov assumption.