Effects of Electronic Correlations for Adiabatic Electrochemical Reactions of Electron Transfer in Electrode Models with Nearly Empty and Nearly Filled Conduction Bands: Adiabatic Free Energy Surfaces

摘要

Adiabatic free energy surfaces (AFES) for adiabatic electrochemical reactions of electron transfer (ARET) are computed with exact allowance for electron-electron correlation effects (EECE) in models of electrode with nearly empty and almost filled conduction bands and analyzed on the basis of a diagram of kinetic modes obtained earlier. The EECE role in ARET for an electrode with an arbitrary Fermi level in a conduction band of an arbitrary width is discussed. In the general case, allowing for EECE gives at some model parameters results other than for the Fermi level coinciding with the conduction band center (model of a surface molecule, MSM). As in the case of MSM considered previously, EECE considerably reduce activation free energies and at some model parameters give qualitatively different AFES.