A Simple ab Initio Model for the Hydrated Electron That Matches Experiment.

Area of Science:

• Physical Chemistry
• Quantum Chemistry
• Computational Chemistry

Background:

• The structure and properties of the hydrated electron have been debated for over 50 years.
• Understanding the hydrated electron is crucial in various chemical and physical processes.

Purpose of the Study:

• To investigate a minimal model for the aqueous electron.
• To determine the dominant structural motif of the hydrated electron.

Main Methods:

• Utilized ab initio calculations with various levels of theory and basis sets.
• Employed a minimal model comprising a small water anion cluster embedded in a polarized continuum.
• Performed calculations on 4-water anion clusters and larger.

Main Results:

• Identified a minimum energy structure for 4-water anion clusters similar to previous simulations.
• The model accurately reproduces resonance Raman properties, radius of gyration, vertical detachment energy, and hydration free energy.
• Successfully calculated EPR g-factor and hyperfine couplings for the first time.

Conclusions:

• The simple tetrahedral anion cluster model aligns well with experimental data.
• This model likely represents the dominant structural motif of the hydrated electron.
• The findings provide significant insights into the fundamental nature of the hydrated electron.