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Spatial Separation of Molecular Conformers and Clusters
Published on: January 9, 2014
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Solvated Electrons in Clusters: Magic Numbers for the Photoelectron Anisotropy
Adam H C West1, Bruce L Yoder1, David Luckhaus1
1ETH Zürich , Laboratory of Physical Chemistry, Vladimir-Prelog-Weg 2, CH-8093 Zürich, Switzerland.
The Journal of Physical Chemistry. A
|September 11, 2015
Summary
Magic numbers in sodium-doped clusters reveal insights into photoelectron anisotropy. Specific numbers were found for ammonia and dimethyl ether, but not water or methanol clusters.
Area of Science:
- Physical Chemistry
- Quantum Chemistry
- Materials Science
Background:
- Magic numbers in atomic and molecular clusters are associated with enhanced stability.
- Photoelectron anisotropy in angle-resolved photoelectron spectra provides information on electronic structure and symmetry.
- Sodium-doped clusters offer a model system to study electronic delocalization and its impact on cluster properties.
Purpose of the Study:
- To investigate the existence and origin of magic numbers in sodium-doped neutral molecular clusters.
- To correlate magic numbers with photoelectron anisotropy in angle-resolved photoelectron spectra.
- To explore the influence of solvent molecules (water, ammonia, methanol, dimethyl ether) on these phenomena.
Main Methods:
- Density functional calculations were employed to model cluster structures and electronic properties.
- Experimental angle-resolved photoelectron spectroscopy was used to measure photoelectron anisotropy.
- Systematic studies were performed on sodium clusters doped with varying numbers of H2O, NH3, CH3OH, and CH3OCH3 molecules.
Main Results:
- Magic numbers were identified at n = 6 for Na(CH3OCH3)n and n = 4 for Na(NH3)n clusters.
- These magic numbers correlated with pronounced anisotropy in photoelectron angular distributions, indicative of delocalized highest occupied molecular orbitals (HOMOs).
- No clear magic numbers related to photoelectron anisotropy were observed for Na(H2O)n and Na(CH3OH)n clusters.
Conclusions:
- The presence of magic numbers in sodium-doped clusters is linked to the delocalization of the HOMO and high symmetry.
- The differing results for water/methanol versus ammonia/dimethyl ether clusters are attributed to variations in hydrogen bonding and the prevalence of structural isomers.
- This study highlights the sensitivity of photoelectron anisotropy to cluster structure and electronic delocalization, providing a new avenue for identifying magic numbers.
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