Reconstruction of potential energy profiles from multiple rupture time distributions

TL;DR

This paper investigates methods to reconstruct molecular potential energy profiles from rupture time data, highlighting the challenges, optimal conditions, and the use of multiple measurements to improve accuracy for complex potentials.

Contribution

It introduces a framework for reconstructing complex potential energy profiles from multiple rupture time distributions, including optimal conditions and heuristic guidelines.

Findings

Reliable reconstruction of barrier height and width from single FPT distribution.

Multiple FPT distributions improve reconstruction of complex potentials with multiple minima.

Optimal bond potential amplitudes enhance numerical reconstruction efficiency.

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.