Nonergodicity in nanoscale electrodes
Literature Information
Diego Krapf
The response of nanoscale electrodes displays deviations from conventional voltammetry theory that include a reduction in the limiting current and enhanced current fluctuations. We study the power spectra of these fluctuations in well characterized conical electrodes with radii between 2 and 10 nm. The fluctuations are found to display non-trivial power laws. We propose a model based on reversible adsorption of the redox species onto the nanoelectrode. This model is consistent with the non-stationary character of both the limiting current and the adsorption of molecules onto metal electrodes. Our model predicts the electrochemical reaction is nonergodic and sets fundamental limits on the sensitivity of uncoated nanoelectrodes.
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.













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