Theoretical study of Al(n)V+ clusters and their interaction with Ar

Area of Science:

• Physical Chemistry
• Materials Science
• Computational Chemistry

Background:

• Experimental studies investigated vanadium (V) impurity sites in aluminum (Al(n)V(+)) clusters using argon interaction.
• Understanding impurity behavior in clusters is crucial for materials design.

Purpose of the Study:

• To computationally investigate the structural and electronic properties of Al(n)V(+) clusters (n=14-21).
• To study the adsorption of argon (Ar) on these V-doped Al clusters.
• To elucidate the exohedral-to-endohedral transition of the V impurity.

Main Methods:

• Density Functional Theory (DFT) calculations.
• Analysis of binding energy per atom, second energy difference, and atom separation energies.
• Simulation of atomic argon adsorption on cluster structures.

Main Results:

• For n < 17, V substitutes a surface Al atom; for n ≥ 17, V becomes embedded, forming fcc-like structures.
• Argon adsorption occurs on surface atoms (V for n < 17, Al for n ≥ 17).
• A significant drop in Ar adsorption energy and increased Ar-cluster distance at n=17 signals a transition to physisorption.

Conclusions:

• Computational results align with experimental observations regarding V impurity site occupation.
• The study confirms a critical size (n=17) for the exohedral-endohedral transition of V in Al clusters.
• The findings provide insights into the nature of Ar-cluster interactions at the transition point.