Theory of electron transfer at electrified interfaces

摘要: Abstract Some recent achievements in condensed phase molecular charge transfer theory are overviewed, with focus on interfacial electrochemical electron (ET). Elements of available and new formalism addressed 2 observations , 3 et . New elements considered are, firstly, a convenient parametric scheme for calculation the rate constant current. The goes beyond commonly used quadratic free energy relations extends straightforwardly to vibrational frequency changes, anharmonic nuclear motion, tunnelling local vibrationally dispersive environmental modes. Other adiabatic processes, self-consistent calculations electronic–vibrational interaction long-range ET. Self-consistency leads non-linear features. These enhance both by increasing electronic tunnel factor decreasing activation Gibbs energy. followed Section 4 discussion theoretical basis several ET systems. Attention is given across well-characterized thin films, hot electrochemistry, electrochemistry at superconducting electrodes, near temperature or field induced high order transition. Particular attention situ scanning microscopy where dielectric continuum configurationally fluctuating water molecules gap, adsorbates, bias voltage overvoltage spectroscopy different mechanisms, considered. 5 gives short some views proton conduction strongly hydrogen bonded systems, dihydrogen evolution reaction, low-temperature This part concluded perspectives areas scale science (nanotechnology, electronics) which can be expected hold cases pure applied theory.