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Spatial Separation of Molecular Conformers and Clusters
Published on: January 9, 2014
Structures and energetics of small lead cluster ions
Rebecca Kelting1, Robin Otterstätter, Patrick Weis
1Abteilung für Physikalische Chemie mikroskopischer Systeme, Karlsruher Institut für Technologie, Kaiserstr. 12, 76128 Karlsruhe, Germany.
The Journal of Chemical Physics
|January 19, 2011
Summary
Structural differences between lead cluster cations and anions were identified using ion mobility and DFT calculations. These findings reveal distinct structural motifs and fragmentation behaviors for lead clusters, crucial for understanding their chemical properties.
Area of Science:
- Physical Chemistry
- Materials Science
- Computational Chemistry
Background:
- Understanding the structural properties of atomic clusters is fundamental to materials science.
- Lead clusters exhibit unique electronic and structural characteristics due to relativistic effects.
- Distinguishing between cationic and anionic cluster structures is essential for predicting reactivity.
Purpose of the Study:
- To determine the specific atomic structures of lead cluster cations and anions.
- To investigate the influence of charge state on lead cluster geometry.
- To correlate calculated structural properties with experimental fragmentation data.
Main Methods:
- Gas phase ion mobility measurements to probe cluster structures.
- Relativistic density functional theory (DFT) calculations with spin-orbit coupling.
- Collision-induced dissociation mass spectrometry to study fragmentation pathways.
Main Results:
- Identified distinct structures for lead clusters (Pb_n, 4 ≤ n ≤ 15) based on charge state.
- Observed charge-dependent structures for hexamer (octahedron anion vs. fused tetrahedra cation) and larger clusters.
- Found strong correlation between calculated fragmentation energies and experimental collision-induced dissociation spectra.
Conclusions:
- Lead cluster structures are highly dependent on size and charge.
- Relativistic DFT calculations accurately predict experimental observations.
- Fragmentation patterns provide insights into the relative stability of different lead cluster structures.
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