Accurate Prediction of One-Electron Reduction Potentials in Aqueous Solution by Variable-Temperature H-Atom...

Area of Science:

• Computational Chemistry
• Electrochemistry
• Quantum Mechanics

Background:

• Calculating reduction potentials for charged species in aqueous solution is crucial for understanding redox processes.
• Existing computational methods often struggle with accuracy for highly charged transition-metal complexes.

Purpose of the Study:

• To present a robust and efficient theoretical approach for calculating reduction potentials of charged species.
• To validate the method's accuracy against experimental data for challenging transition-metal complexes.

Main Methods:

• Employing thermodynamic cycles involving H-atom addition/abstraction to relate charged species to their neutralized counterparts.
• Separating one-electron reduction from protonation/deprotonation using temperature dependence analysis.

Main Results:

• The developed method shows excellent agreement with experimental electrochemical data for 15 transition-metal complexes.
• The approach provides accurate reduction potentials for systems previously considered challenging for computational electrochemistry.

Conclusions:

• The presented theoretical approach offers a reliable and efficient tool for computational electrochemistry.
• This method advances the accurate prediction of redox properties for complex charged species in solution.