Charge distribution analysis in Ag(n)(m⁺) clusters: molecular modeling and DFT calculations

Area of Science:

• Physical Chemistry
• Materials Science
• Computational Chemistry

Background:

• Silver clusters exhibit unique properties influenced by size and charge.
• Understanding charge distribution in metallic clusters is crucial for predicting their behavior.

Purpose of the Study:

• Investigate the structural and charge properties of neutral and charged silver clusters (Ag₆₃ and Ag₁₁₃).
• Analyze how increasing charge affects cluster deformation and surface charge distribution.
• Validate the accuracy of the embedded-atom force field and charge equilibrium approach.

Main Methods:

• Simulated annealing molecular dynamics simulations were employed.
• Density-functional theory calculations were used for natural population analysis.
• Comparison between simulation results and theoretical calculations.

Main Results:

• Silver clusters (Ag₆₃ and Ag₁₁₃) deform with increasing charge to better accommodate surface charges.
• Surface charges are heterogeneously distributed, influenced by electrostatic repulsion and atomic under-coordination.
• The embedded-atom force field combined with the charge equilibrium approach accurately reproduces atomic charges.

Conclusions:

• The study demonstrates the significant impact of charge on silver cluster structure.
• The computational methods used are suitable for studying charged metallic clusters.
• Findings provide insights into the behavior of charged silver nanoparticles.