Density-Based Descriptors of Redox Reactions Involving Transition Metal Compounds as a Reality-Anchored Framework: A Perspective

Description of redox reactions is critically important for understanding and rational design of materials for electrochemical technologies, including metal-ion batteries, catalytic surfaces, or redox-flow cells. Most of these technologies utilize redox-active transition metal compounds due to their rich chemistry and their beneficial physical and chemical properties for these types of applications. A century since its introduction, the concept of formal oxidation states (FOS) is still widely used for rationalization of the mechanisms of redox reactions, but there exists a well-documented discrepancy between FOS and the electron density-derived charge states of transition metal ions in their bulk and molecular compounds. We summarize our findings and those of others which suggest that density-driven descriptors are, in certain cases, better suited to characterize the mechanism of redox reactions, especially when anion redox is involved, which is the blind spot of the FOS ansatz.

Automated summary

Density-driven descriptors are more suitable for characterizing the mechanism of redox reactions than formal oxidation states, especially when anion redox is involved. The description of redox reactions is critically important for understanding and rational design of materials for electrochemical technologies.