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Structural changes of Pd13 upon charging and oxidation/reduction
J Ulises Reveles1, A M Köster, P Calaminici
1Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284-2000, USA. jureveles@vcu.edu
The Journal of Chemical Physics
|March 27, 2012
Summary
This study reveals palladium cluster structures: cationic Pd(13)(+) prefers C(s) geometry, while anionic Pd(13)(-) and neutral Pd(13)O(2) favor compact ~I(h) structures. A structural oscillation is predicted during oxidation/reduction cycles.
Area of Science:
- Computational Chemistry
- Materials Science
- Surface Science
Background:
- Palladium clusters are crucial in catalysis.
- Understanding their structural and electronic properties is key to designing efficient catalysts.
- The influence of charge and oxidation state on cluster stability is not fully understood.
Purpose of the Study:
- To investigate the structural stability of cationic, anionic, and neutral palladium oxide clusters.
- To elucidate the electronic factors governing the preferred geometries.
- To predict structural dynamics during redox processes.
Main Methods:
- First-principle density functional theory (DFT) calculations.
- Generalized Gradient Approximation (GGA) for exchange-correlation functional.
- Analysis of electronic structure, including cluster orbitals and atomic orbital hybridization.
Main Results:
- Cationic Pd(13)(+) adopts a C(s) geometry, similar to neutral Pd(13).
- Anionic Pd(13)(-) and neutral Pd(13)O(2) exhibit a stable compact ~I(h) structure.
- Electronic structure analysis highlights the role of delocalized cluster orbitals and Pd-O hybridization in stabilizing geometries.
- A structural oscillation between C(s) and ~I(h) isomers is predicted for Pd(13) during redox cycles with low energy barriers (0.3-0.4 eV).
Conclusions:
- The charge state significantly impacts the preferred geometry of Pd(13) clusters.
- Oxygen incorporation in Pd(13)O(2) promotes a compact, symmetric structure.
- Electronic structure plays a critical role in determining cluster stability and isomer ordering.
- Pd(13) clusters are predicted to undergo reversible structural changes during oxidation and reduction, relevant for catalytic applications.
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