J Phys Chem Lett. 2023 Nov 30:10935-10942. doi: 10.1021/acs.jpclett.3c02643. Online ahead of print.
ABSTRACT
Break junction experiments allow investigating electronic and spintronic properties at the atomic and molecular scale. These experiments generate by their very nature broad and asymmetric distributions of the observables of interest, and thus, a full statistical interpretation is warranted. We show here that understanding the complete lifetime distribution is essential for obtaining reliable estimates. We demonstrate this for Au atomic point contacts by adopting Bayesian reasoning to make maximal use of all measured data to reliably estimate the distance to the transition state, x‡, the associated free energy barrier, ΔG‡, and the curvature, v, of the free energy surface. Obtaining robust estimates requires less experimental effort than with previous methods and fewer assumptions and thus leads to a significant reassessment of the kinetic parameters in this paradigmatic atomic-scale structure. Our proposed Bayesian reasoning offers a powerful and general approach when interpreting inherently stochastic data that yield broad, asymmetric distributions for which analytical models of the distribution may be developed.
PMID:38035375 | DOI:10.1021/acs.jpclett.3c02643
