Please use this identifier to cite or link to this item: https://hdl.handle.net/2440/50875
Type: Thesis
Title: Threshold photo-ionisation and density functional theory studies of metal-carbide clusters.
Author: Dryza, Viktoras
Issue Date: 2008
School/Discipline: School of Chemistry and Physics : Chemistry
Abstract: Neutral gas-phase metal-carbide clusters are generated by laser ablation and are detected in the constructed time-of-flight mass-spectrometer by laser ionisation. Photo-ionisation efficiency (PIE) experiments are performed on the metal-carbide clusters to determine their ionisation potentials (IPs). Complimentary density functional theory (DFT) calculations are performed on the energetically favorable structural isomers of the metalcarbide clusters. Comparison between the calculated IPs of the isomers and the experimental IP allows the carrier of the observed ionisation onset for a metal-carbide cluster to be assigned. The niobium-carbide clusters Nb₃Cy (y = 0–4), Nb₄Cy (y = 0–6) and Nb₅Cy (y = 0–6) are examined by PIE experiments and DFT calculations. The IPs of the niobium-carbide clusters are found to be either left reasonably unchanged from the IPs of the bare metal clusters or moderately reduced. The clusters Nb₃C₂, Nb₄C₄, Nb₅C₂ and Nb₅C₃ display the largest IP reductions for their corresponding cluster series. The structures assigned to the IPs of the Nb₃Cy (y = 1–3) clusters are based on the carbon atoms attaching to the niobium faces and/or niobium-niobium edges of the triangular Nb₃ cluster. However, for Nb₃C₄ the ionisation onset is assigned to a low-lying isomer, which contains a molecular C₂ unit, rather than the lowest energy isomer, a niobium atom deficient 2×2×2 face-centred cubic (fcc) nanocrystal structure. The structures assigned to the IPs of the Nb₄Cy (y = 1–4) clusters are based on the carbon atoms attaching in turn to the niobium faces of the tetrahedral Nb₄ cluster, developing a 2×2×2 fcc nanocrystal structure for Nb₄C₄. For Nb₄C₃ two ionisation onsets are observed; one weak onset at low energy and another more intense onset at high energy. It is proposed that the two onsets are due to ionisation from both a metastable ³A₁ state and the ground ¹A₁ state of the lowest energy isomer. The ionisation onsets of Nb₄C₅ and Nb₄C₆ are also proposed to originate from metastable triplet states of the lowest energy isomers, with the transitions from the ground singlet states calculated to be greater than the highest achievable photon energy in the laboratory. The structures of Nb₄C₅ and Nb₄C₆ have one and two carbon atoms in a 2×2×2 fcc nanocrystal substituted with molecular C₂ units, respectively. The structures assigned to the IPs of the Nb₅Cy (y = 1–6) clusters are based on the underlying Nb₅ cluster being in either a “prolate” or “oblate” trigonal bipyramid geometry; the former has six niobium faces available for carbon addition, while the latter has two niobium butterfly motifs and two niobium faces available for carbon addition. Both the structures of Nb₅C₅ and Nb₅C₆ have the underlying Nb₅ cluster in the oblate trigonal bipyramid geometry and contain one and two molecular C₂ units, respectively. The tantalum-carbide clusters Ta₃Cy (y = 0–3), Ta₄Cy (y = 0–4) and Ta₅Cy (y = 0–6) are examined by PIE experiments and DFT calculations. The IPs of the tantalum-carbide clusters in each series show trends that are very similar to the corresponding iso-valent niobium-carbide cluster series, although the IP reductions upon carbon addition are smaller for the former. For the vast majority of tantalum-carbide clusters, the same structural isomer is assigned to the ionisation onset as that assigned for the corresponding niobium-carbide cluster. Bimetallic tantalum-zirconium-carbide clusters are generated using a constructed double ablation cluster source. The Ta₃ZrCy (y = 0–4) clusters are examined by PIE experiments and DFT calculations. The IP trend for the Ta₃ZrCy cluster series is reasonably similar to that of the Ta₄Cy cluster series, although the IP reductions upon carbon addition are greater for the former. The structures assigned to the IPs of the Ta₃ZrCy (y = 1–4) clusters are based on the carbon atoms attaching in turn to the metal faces of the tetrahedral Ta₃Zr cluster. In summary, the work presented in this thesis demonstrates that the structures of metalcarbide clusters can be inferred by the determination of their IPs through PIE experiments in combination with DFT calculations on candidate structural isomers.
Advisor: Metha, Gregory Francis
Buntine, Mark
Dissertation Note: Thesis (Ph.D.) - University of Adelaide, School of Chemistry and Physics, 2008
Keywords: laser spectroscopy; ionization potential; metal cluster; DFT; nanocrystal; isomer; met-car
Provenance: Copyright material removed from digital thesis. See print copy in University of Adelaide Library for full text.
Appears in Collections:Research Theses

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03chapters6-7.pdf2.22 MBAdobe PDFView/Open
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