Significant bonding rearrangements triggered by Mg₄ clusters.

Area of Science:

• Computational chemistry
• Materials science
• Quantum chemistry

Background:

• Magnesium clusters are of interest due to their unique electronic properties.
• Understanding interactions with Lewis bases is crucial for predicting material behavior.

Purpose of the Study:

• Investigate the structure, stability, and bonding of Mg4 clusters with Lewis bases.
• Explore the electronic properties and reactivity of the resulting complexes.
• Assess the potential catalytic applications of magnesium nanostructures.

Main Methods:

• High-level G4 single-reference calculations.
• CASPT2 multireference formalisms.
• Density functional theory (DFT) for electronic structure analysis.

Main Results:

• Mg4 clusters exhibit high electrophilicity, forming stable adducts with ammonia, water, and hydrogen fluoride.
• Hydrogen shifts from Lewis bases to Mg4 atoms lead to enhanced stability.
• Formation of a stable scaffold with nitrogen or oxygen covalently tetracoordinated to four Mg atoms in ammonia and water complexes.
• Metallic bonding within the Mg4 moiety remains largely unaltered post-adduct formation.

Conclusions:

• The reactivity of Mg4 clusters suggests potential for catalytic applications.
• The observed stable structures indicate unique bonding characteristics of magnesium nanoclusters.
• Further research into magnesium nanostructures could yield novel catalysts.