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Related Experiment Video

Updated: Feb 2, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
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Bare versus protected tetrairidium clusters by density functional theory.

Maurício J Piotrowski1, Glaucio R Nagurniak, Eder H da Silva

  • 1Department of Physics, Federal University of Pelotas, PO Box 354, 96010-900, Pelotas, RS, Brazil. mauriciomjp@gmail.com.

Physical Chemistry Chemical Physics : PCCP
|November 21, 2018
PubMed
Summary
This summary is machine-generated.

Tetrairidium (Ir4) clusters exhibit varying stability based on their chemical environment. Ligands like CO, O2, and PH3 favor tetrahedral structures, while SH2 prefers square planar configurations for Ir4 nanoclusters.

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Area of Science:

  • Computational chemistry
  • Materials science
  • Catalysis

Background:

  • Tetrairidium (Ir4) clusters are crucial subnanometric catalysts with high activity and stability.
  • Catalytic properties of nanoclusters depend on size, shape, and environmental interactions.
  • Atomistic-level understanding is essential for optimizing Ir4 cluster performance.

Purpose of the Study:

  • Investigate the energetic stability of Ir4 clusters in various chemical environments (bare vs. protected).
  • Determine the preferred isomeric configurations (square planar vs. tetrahedral) under different ligand interactions.
  • Analyze the bonding and electronic structure to understand structure-property relationships.

Main Methods:

  • Density Functional Theory (DFT) calculations.
  • Generalized Gradient Approximation (GGA) with van der Waals (vdW) corrections.
  • All-electron projected augmented wave (PAW) method with spin-orbit coupling (SOC).
  • Energy Decomposition Analysis (EDA).

Main Results:

  • The square planar isomer is the most stable for bare Ir4 clusters.
  • Tetrahedral Ir4 clusters are most stable with CO, O2, and PH3 ligands.
  • The square planar motif remains most stable for Ir4 clusters protected by SH2 ligands.
  • Ligand environment significantly alters Ir4 cluster geometry and electronic structure.

Conclusions:

  • The chemical environment dictates the preferred isomeric structure of Ir4 nanoclusters.
  • Tetrahedral motifs exhibit weakened sigma and pi bonds compared to square planar structures.
  • Understanding these structure-environment interactions is key to designing advanced Ir4 catalysts.