Optical transitions of symmetrical mixed-valence systems in the Class Ⅱ-Ⅲ transition regime

摘要

In the Robin and Day classification, mixed-valence systems are characterized as Class Ⅰ, Ⅱ or Ⅲ depending on the strength of the electronic interaction between the oxidized and reduced sites, ranging from essentially zero (Class Ⅰ), to moderate (Class Ⅱ), to very strong electronic coupling (Class Ⅲ). The properties of Class Ⅰ systems are essentially those of the separate sites. Class Ⅱ systems possess new optical and electronic properties in addition to those of the separate sites. However, the interaction between the sites is sufficiently weak that Class Ⅱ systems are valence trapped or charge localized and can the be described by a doublewell potential. In Class Ⅲ systems the interaction of the donor and acceptor sites is so great that two separate minima are no longer discernible and the energy surface features a single minimum. The electron is delocalized and the system has its own unique properties. The Robin and Day classification has enjoyed considerable success and most of the redox systems studied to date are readily assigned to Class Ⅱ. However the situation becomes much more complicated when the system shows borderline Class Ⅱ/Ⅲ behavior. Such "almost delocalized" mixed-valence systems are difficult to characterize. In this article spectral band shapes and intensities are calculated utilizing increasingly complex models including two to four states. Free-energy surfaces are constructed for harmonic diabatic surfaces and characterized as a function of increasing electronic coupling to simulate the Class Ⅱ to Ⅲ transition. The properties of the charge-transfer absorption bands predicted for borderline mixed-valence systems are compared with experimental data. The treatment is restricted to symmetrical (ΔG~0 = 0) systems.