An important impact of the molecule–electrode coupling asymmetry on the efficiency of bias-driven redox processes in molecular junctions
Literature Information
Two recent experimental and theoretical studies (Proc. Natl. Acad. Sci. U. S. A., 2014, 111, 1282–1287; Phys. Chem. Chem. Phys., 2014, 16, 25942–25949) have addressed the problem of tuning the molecular charge and vibrational properties of single molecules embedded in nanojunctions. These are molecular characteristics escaping so far from an efficient experimental control in broad ranges. Here, we present a general argument demonstrating why, out of various experimental platforms possible, those wherein active molecules are asymmetrically coupled to electrodes are to be preferred to those symmetrically coupled for achieving a(n almost) complete redox process, and why an electrochemical environment has advantages over “dry” setups. This study aims at helping to nanofabricate molecular junctions using the most appropriate platforms allowing the broadest possible bias-driven control over the redox state and vibrational modes of single molecules linked to electrodes.
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Physical Chemistry Chemical Physics

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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