Effects of tip-induced material reorganization in dynamic force spectroscopy

Dynamic force spectroscopy (DFS) has become a well-established method for characterizing bond strength, yet may also be useful for examining more complex phenomena such as dynamic processes or multiple reaction pathways. Here, we analyze the case where contact between an atomic force microscopy (AFM) tip and the sample induces sample reorganization during testing. Surface contact often causes molecular rearrangement in soft materials, which could also result in an altered reaction energy landscape. We model this situation by allowing the energy barrier position and magnitude to be time-dependent functions with a characteristic time scale τ . We find dynamic energy barriers result in two linear regimes with a dramatic transition near t=τ in the DFS analysis. The sharp transition region is a hallmark of a moving energy barrier and indicates the time scale of reorganization. These results illustrate that DFS may be useful to monitor dynamic transitions and also highlight the importance of extending the loading rate range used in DFS studies.