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Stability of small cationic platinum clusters.

Piero Ferrari1, Klavs Hansen, Peter Lievens

  • 1Laboratory of Solid State Physics and Magnetism, KU Leuven, 3001 Leuven, Belgium. ewald.janssens@kuleuven.be.

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|November 21, 2018
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Summary
This summary is machine-generated.

Small platinum clusters show enhanced stability at the platinum tetramer (Pt4+) size. This stability, observed through photofragmentation, is explained by computational analysis of dissociation energies and electronic structure.

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Computational Chemistry

Background:

  • Understanding the stability of small metal clusters is crucial for catalysis and materials science.
  • Platinum clusters are of particular interest due to their catalytic properties.
  • Previous studies have indicated size-dependent properties in metal clusters.

Purpose of the Study:

  • To investigate the relative stability of small cationic platinum clusters.
  • To determine the factors contributing to enhanced stability in specific cluster sizes.
  • To correlate experimental observations with theoretical calculations.

Main Methods:

  • Photofragmentation experiments were used to probe cluster stability.
  • Mass spectrometry was employed to analyze fragment ions.
  • Density functional theory (DFT) calculations were performed to compute dissociation energies and electronic structures.

Main Results:

  • Mass spectra revealed a local intensity minimum at Pt5+, indicating enhanced stability for the platinum tetramer (Pt4+).
  • Radiative cooling was found to be negligible on the experimental timescale for clusters in the N = 3-8 size range.
  • Calculated dissociation energies using DFT accurately explained the experimental mass spectra.
  • A large calculated HOMO-LUMO gap (∼1.2 eV) for Pt4+ was attributed to its highly symmetric structure.

Conclusions:

  • The platinum tetramer (Pt4+) exhibits enhanced stability due to its highly symmetric structure.
  • The observed stability is well-explained by DFT-computed dissociation energies.
  • The large HOMO-LUMO gap of Pt4+ correlates with its low reactivity in gas-phase reactions.