In this thesis, bare and thiolate-protected gold nanoclusters and thiolated polymeric
gold, silver and copper complexes are computationally studied by using density functional
codes GPAW (grid projector augmented wave) and CPMD (Car-Parrinello
molecular dynamics and metadynamics). Since 2007, breakthroughs in experimental
structural determination of Au25(SR)−1
18 and Au102(SR)44 clusters (SR = thiolate)
have revised the understanding of bonding motifs at the gold-sulfur nano-interface.
The structure of both clusters can be written via a "Divide and Protect" structural
motif as AuNcore[Aux(SR)x+1]y where a considerable number of Au atoms of the cluster
are outside of the metal core, covalently bound with thiolates in the protective ligand
layer. The Au25 cluster can be written as Au13[Au2(SR)3]−1
6 featuring an approximately
icosahedral Au13 core and six oligomeric Au2(SR)3 units or "semi-rings". The
comparative analysis of thiolated Cu, Ag, and Au complexes, related to th
e "semirings",
shows that the metal-thiolate bond is sterically flexible, i.e., ring-like, helixlike
or catenane-like complexes are energetically competitive for homoleptic complexes
(MeSM)x, where x ≤ 12 (Me is methyl and M = Cu, Ag, Au). Among these complexes,
the gold-thiolate bond is dominantly covalent with a slight electron charge transfer to
sulfur and the copper-thiolate bond is most ionic among the three. The stability of
the Au25 nanocluster can be understood from electron-shell-closing arguments. In its
anionic form the cluster has 8 Au(6s) electrons in the metal core, composing a shell
closing of P-type and rendering the cluster as a closed shell "superatom". Chemical
modifications of the Au25 cluster was investigated by (i) replacing one Au atom by
a Pd atom in the metal core or in the ligand shell, or by (ii) changing the nature
of a simple methylthiolate ligand to more electronegative by chlorination. Both of
these studies were motivated by experimental work and are helpful in interpreting the
structural and electrochemical behaviour of doped clusters. The Au25 cluster, either in
its all-gold or doped form, is a robust building block that could be used for designing
cluster-based nanomaterials with tunable electronic, optical or magnetic properties.
Finally, catalytic properties of (i) small, bare and neutral gold clusters (Au2 and Au4)
for H2O2 formation and (ii) activated, partially thiolate-protected Au25 clusters for
CO oxidation were studied. Reaction pathways for competing channels in H2O2 (hydrogen
peroxide or water formation) were studied by room-temperature molecular
dynamics and metadynamics. It was concluded that small gold clusters are fluxional
(their structure can change during the reactions) and the size of the gold cluster can
affect the probability of a given reaction channel. Activation of the Au25 cluster by
partial removal of the protective layer changes the electron count in the metal core
and renders the cluster an electropositive species that can bind molecular oxygen and
produce CO2 with considerably low (below 0.7 eV) activation barriers.
...
