Structural transformation in Pd nanoclusters induced by Cu doping: an ADFT study

Area of Science:

• Computational materials science
• Nanoparticle research
• Quantum chemistry

Background:

• Transition metal nanoparticles are crucial for energy, electronics, medicine, and agriculture.
• Doping is a key strategy to enhance nanoparticle properties beyond those of pure materials.
• Understanding doping effects in larger nanoclusters ( >16 atoms) is essential for advanced applications.

Purpose of the Study:

• To theoretically investigate the structural and electronic properties of pure Pd19, Pd18Cu, and Pd17Cu2 nanoclusters.
• To elucidate the role of copper doping on the stability and reactivity of palladium nanoclusters.
• To explore doping effects in nanoclusters larger than those previously studied.

Main Methods:

• Auxiliary Density Functional Theory (ADFT) calculations using the deMon2k code.
• Structure optimization without symmetry restrictions via Born-Oppenheimer Molecular Dynamics (BOMD).
• Calculation of energetic and electronic properties, including binding energy and HOMO-LUMO gap.

Main Results:

• A structural transition occurs in Pd17Cu2, shifting from icosahedral (Pd19, Pd18Cu) to a double-icosahedral-base structure.
• Binding energy per atom increases with higher copper concentration in the nanoclusters.
• Chemical reactivity, indicated by the HOMO-LUMO gap, increases with increasing copper content.

Conclusions:

• Copper doping significantly influences the structure and stability of palladium nanoclusters.
• Increased copper content leads to enhanced binding energy and chemical reactivity.
• These findings provide insights into designing advanced doped palladium nanoclusters for various applications.