Reconstruction of potential energy profiles from multiple rupture time distributions

Abstract: We explore the mathematical and numerical aspects of reconstructing a potential energy profile of a molecular bond from its rupture time distribution. While reliable reconstruction of gross attributes, such as the height and the width of an energy barrier, can be easily extracted from a single first passage time (FPT) distribution, the reconstruction of finer structure is ill-conditioned. More careful analysis shows the existence of optimal bond potential amplitudes (represented by an effective Peclet number) and initial bond configurations that yield the most efficient numerical reconstruction of simple potentials. Furthermore, we show that reconstruction of more complex potentials containing multiple minima can be achieved by simultaneously using two or more measured FPT distributions, obtained under different physical conditions. For example, by changing the effective potential energy surface by known amounts, additional measured FPT distributions improve the reconstruction. We demonstrate the possibility of reconstructing potentials with multiple minima, motivate heuristic rules-of-thumb for optimizing the reconstruction, and discuss further applications and extensions.