Octahedral Coordinated Cluster TaN₁₂ ⁺: Mass Spectrometry Detection, Photodissociation Observation, and Theoretical...

Area of Science:

• Materials Science
• Computational Chemistry
• Physical Chemistry

Background:

• Tantalum nitride (TaN) clusters are of interest for their unique electronic and magnetic properties.
• Understanding the structure-property relationships of these clusters is crucial for developing novel materials.

Purpose of the Study:

• To synthesize and characterize TaN_n⁺ cationic clusters.
• To investigate the structural, electronic, and magnetic properties of the dominant TaN₁₂⁺ cluster.
• To elucidate the photodissociation pathways and bonding characteristics of TaN₁₂⁺.

Main Methods:

• Laser ablation for cluster generation.
• Time-of-flight mass spectrometry for identification.
• Photodissociation experiments with 266 nm photons.
• Density functional theory (DFT) calculations for structural and electronic analysis.
• Hirshfeld charge and spin-density analyses.

Main Results:

• TaN₁₂⁺ was identified as the most abundant cluster.
• Photodissociation predominantly yielded TaN₄⁺.
• DFT calculations revealed an octahedral D_4h structure for TaN₁₂⁺ with six N₂ ligands.
• Asymmetric Ta-N bonding was attributed to σ and π interactions of N₂ ligands.
• The cluster exhibits ferrimagnetic properties due to antiparallel spin coupling.
• Ta acts as a Lewis acid, and N₂ ligands act as Lewis bases.

Conclusions:

• The study provides a comprehensive understanding of the TaN₁₂⁺ cluster's structure, bonding, and magnetic behavior.
• The reversible growth-dissociation pathways of TaN_2n⁺ clusters were established.
• The findings contribute to the fundamental knowledge of transition metal nitride cluster chemistry and magnetism.