Excess electron in water at different thermodynamic conditions

Area of Science:

• Physical Chemistry
• Computational Chemistry
• Quantum Chemistry

Background:

• Understanding the behavior of excess electrons in water is crucial for various chemical and biological processes.
• Previous studies have explored electron localization, but a comprehensive understanding across different densities and temperatures is still developing.

Purpose of the Study:

• To investigate the localization of hydrated electrons in water across a range of densities and temperatures.
• To develop a method for identifying the electron wavefunction's localization region using molecular dipole moments.
• To analyze the impact of self-interaction corrections on optical absorption spectra.

Main Methods:

• Density functional-based molecular dynamics simulations were employed.
• Analysis of spatial variations in water molecule dipole moments.
• Comparison with experimental data and path integral molecular dynamics calculations.

Main Results:

• Electron localization persists even at very low water densities.
• A novel algorithm was proposed to correlate H2O dipole moment orientation with electron wavefunction localization.
• Weighted subtraction of self-interaction errors significantly improved the accuracy of predicted optical absorption peaks.

Conclusions:

• The study confirms electron localization in water under diverse conditions.
• The developed algorithm offers a new tool for understanding electron solvation dynamics.
• Self-interaction correction strategies are vital for accurate prediction of hydrated electron properties.