Generalized cluster states based on finite groups

We define generalized cluster states based on finite group algebras in analogy to the generalization of the toric code to the Kitaev quantum double models. We do this by showing a general correspondence between systems with CSS structure and finite group algebras, and applying this to the cluster states to derive their generalization. We then investigate properties of these states including their projected entangled pair state representations, global symmetries, and relationship to the Kitaev quantum double models. We also discuss possible applications of these states.

Trapping phosphorus (III) into polyoxometalates: synthesis, characterisation and electronic behaviour study

The introduction of electronically-active heteroanions into polyoxometalates (POMs) is one of the emerging topics in this field. The novel clusters have shown unprecedented intramolecular electron-transfer features that can be directly mediated by the incorporated heteroanions. In this thesis, we will focus on the study of phosphite (HPO32-) as new non-traditional heteroanions, discover HPO32- templated nanostructures, investigate their electronic behaviours as well as understand the self-assembly process of HPO32--templated species. The thesis starts with incorporating HPO32- into POM cages. The feasibility of this work was illustrated by the successful trapping of HPO32- into a “Trojan Horse” type {W18O56} nanocage. The reactivity of embedded {HPO3} was fully studied, showing the cluster undergoes a structural rearrangement in solution whereby the {HPO3} moieties dimerise to form a weakly interacting (O3PH···HPO3) moiety. In the crystalline state a temperature-dependent intramolecular redox reaction and structural rearrangement occurs. This rearrangement appears to proceed via an intermediate containing two different templates, a pyramidal {HPO3} and a tetrahedral {PO4} moiety. {HPO3} templated POM cages were then vigorously expanded and led to the isolation of five either fully oxidised or mixed-valence clusters trapped with mono-, di-, or tri- {HPO3}. Interestingly, an intriguing 3D honeycomb-like host-guest structure was also synthesised. The porous framework was self-aggregated by a tri-phopshite anion templated {W21} cluster with a {VO4} templated Wells-Dawson type {W18} acting as a guest species within the hexagonal channels. Based on this work, we further extended the templating anions to two different redox-active heteroanions, and discovered a unique mixed-heteroatom templated system built by pairing redox-active {HPIIIO3} with {TeO3}, {SeO3} or {AsO3}. Two molecular systems were developed, ie. “Trojan Horse” type [W18O56(HPO3)0.8(SeO3)1.2(H2O)2]8- and cross-shaped [H4P4X4W64O224]32-/36-, where X=TeIV, SeIV, AsIII. In the case of {W18(HPO3)0.8(SeO3)1.2}, the compound is found to be a mixture of heteroleptic {W18(HPO3)(SeO3)} and homoleptic {W18(SeO3)2} and {W18(HPO3)2}, identified by single crystal x-ray diffraction, NMR as well as high resolution mass spectrometry. The cluster exhibited similar temperature-dependent electronic features to “Trojan Horse” type {W18(HPO3)2O56}. However, due to the intrinsic reactivity difference between {HPO3} and {SeO3}, the thermal treatment leads to the formation of an unusual species [W18O55(PO4)(SeO3)]5-, in which {HPO3} was fully oxidised to {PO4} within the cage, whereas and lone-pair-containing {SeO3} heteroanions were kept intact inside the shell. This finding is extremely interesting, as it demonstrated that multiple and independent intramolecular electronic performance can be achieved by the coexistence of distinct heteroatoms within a single molecule. On the other hand, the cross-shaped [H4P4X4W64O224]32-/36- were constructed by four {W15(HPO3)(XO3)} building units linked by four {WO6} octahedra. Each building unit traps two different heteroatoms. It is interesting to note that the mixed heteroatom species show self-sorting, with a highly selective positional preference. Smaller ionic sized {HPO3} are self-organised into the uncapped side of {W15} cavity, whereas closed side are occupied by larger heteroatoms, which is surprisingly opposed to steric hindrance. Density functional theory (DFT) calculations are currently underway to have a full understanding of the preference of heteroatom substitutions. This series of clusters is of great interest in terms of achieving single molecule-based heteroatom-dependent multiple levels of electron transfer. It has opened a new way to design and synthesise POMs with higher diversity of electrical states, which may lead to a new type of Q-bits for quantum computing. The third chapter is focused on developing polyoxotungstate building blocks templated by {HPO3}. A series of building blocks, {W15O48(HPO3)2}, {W9O30(HPO3)} {W12O40(HPO3)2} and hexagonal {W6O18(HPO3)} have been obtained. The first four building blocks have been reported with {SeO3} and/or {TeO3} heteroanions. This result demonstrates {HPO3} has a similar reactivity as {SeO3} and {TeO3}, therefore studying the self-assembly of {HPO3}-based building blocks would be helpful to have a general understanding of pyramidal heteroatom-based molecular systems. The hexagonal {W6O18(HPO3)} is observed for the first time in polyoxotungstates, showing some of reactivity difference between {HPO3} and {SeO3} and {TeO3}. Furthermore, inorganic salts and pH values have some directing influence on the formation and transformation of various building blocks, resulting in the discovery of a family of {HPO3}-based clusters with nuclearity ranging from {W29} to {W106}. High resolution mass spectrometry was also carried out to investigate the cluster solution behaviour and also gain information of building block speciation. It is found that some clusters experienced decomposition, which gives rise to potential building blocks accountable for the self-assembly.

Exact solutions for cluster-growth kinetics with evolving size and shape profiles

In this paper we construct a model for the simultaneous compaction by which clusters are restructured, and growth of clusters by pairwise coagulation. The model has the form of a multicomponent aggregation problem in which the components are cluster mass and cluster diameter. Following suitable approximations, exact explicit solutions are derived which may be useful for the verification of simulations of such systems. Numerical simulations are presented to illustrate typical behaviour and to show the accuracy of approximations made in deriving the model. The solutions are then simplified using asymptotic techniques to show the relevant timescales of the kinetic processes and elucidate the shape of the cluster distribution functions at large times.

STORM - a novel information fusion and cluster interpretation technique

Analysis of data without labels is commonly subject to scrutiny by unsupervised machine learning techniques. Such techniques provide more meaningful representations, useful for better understanding of a problem at hand, than by looking only at the data itself. Although abundant expert knowledge exists in many areas where unlabelled data is examined, such knowledge is rarely incorporated into automatic analysis. Incorporation of expert knowledge is frequently a matter of combining multiple data sources from disparate hypothetical spaces. In cases where such spaces belong to different data types, this task becomes even more challenging. In this paper we present a novel immune-inspired method that enables the fusion of such disparate types of data for a specific set of problems. We show that our method provides a better visual understanding of one hypothetical space with the help of data from another hypothetical space. We believe that our model has implications for the field of exploratory data analysis and knowledge discovery.

As dinâmicas dos clusters como potenciadoras da competitividade empresarial regional : o caso do cluster hortícola do Ribatejo & Oeste : análise comparativa com Almeria (Espanha)

Mestrado em Gestão e Estratégia Industrial

Ligand effects on the structure and vibrational properties of the thiolated Au18 cluster

Most of the studies devoted to thiolated gold clusters suppose that their core and Au-S framework do not suffer from distortion independently of the protecting ligands (-SR) and it is assumed as correct to simplify the ligand as SCH3. In this work is delivered a systematic study of the structure and vibrational properties (IR and Raman) of the Au18(SR)14 cluster. The pursued goal is to understand the dependency of the displayed vibrational properties of the thiolated Au18 cluster with the ligands type. A set of six ligands was considered during calculations of the vibrational properties based on density functional theory (DFT) and in its dispersioncorrected approach (DFT-D)

On the structure of the Au18(SR)14 cluster

First principles calculations are used for a systematic search of the lowest-energy (most-stable) structure of the recently synthesized Au18(SR)14 cluster. A comparison of the calculated optical absorption and electronic circular dichroism spectra, which are highly sensitive to the cluster structure and chirality, with the experimental spectra of the glutathione-protected gold cluster, Au18(SG)14, is used to discriminate between low-energy isomers of the Au18(SR)14 (R = CH3) cluster. From the good agreement between calculated and measured spectra, it is predicted that the structure of the Au18(SR)14 cluster consists of a prolate Au8 core covered with two dimer (SR–Au–SR–Au–SR) and two trimer (SR–Au–SR–Au–SR–Au–SR) motifs. These results provide additional evidence on the existence of longer trimer motifs as protecting units of small thiolated gold clusters.

Effect of pre-bloom leaf defoliation on cluster morphology and disease pressure

Mestrado Vinifera Euromaster - Instituto Superior de Agronomia - UL

Monitoraggio attivo di un cluster di Raspberry Pi

In questa tesi viene trattata la selezione ed implementazione di un software che permetta di effettuare il monitoraggio e l'invio di segnalazioni automatiche di allerta per un cluster composto da dispositivi aventi capacità computazionali ridotte.

Octahedral molybdenum cluster complexes with aromatic sulfonate ligands

This article describes the synthesis, structures and systematic study of the spectroscopic and redox properties of a series of octahedral molybdenum metal cluster complexes with aromatic sulfonate ligands (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] (where X- is Cl-, Br- or I-; OTs- is p-toluenesulfonate and PhSO3 - is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (>0.6) and narrowest emission bands were found for complexes with a {Mo6I8}4+ cluster core. Moreover, cyclic voltammetric studies revealed that (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] confer enhanced stability towards electrochemical oxidation relative to corresponding starting complexes (nBu4N)2[{Mo6X8}X6].

Photoluminescent materials based on PMMA and a highly-emissive octahedral molybdenum metal cluster complex

Materials that combine photoluminescence, optical transparency and facile processability are of high importance in many applications. This article reports on the development of photoluminescent poly(methyl methacrylate) materials based on novel highly emissive anionic molybdenum cluster complex [{Mo6I8}(OTs)6]2- (where OTs- is the p-toluenesulfonate ion). The materials were obtained by both solution and bulk copolymerisation of methyl methacrylate and (dMDAEMA)2[{Mo6I8}(OTs)6], where dMDAEMA+ is the polymerisable cation [2-(methacryloyloxy)ethyl]dimethyl-dodecylammonium. Evaluation of the resultant hybrid materials showed that one could combine the excellent photoluminescent properties of the cluster complex with the transparency and processability of PMMA.

The SHIVir Survey: A Dynamical Catalogue of Virgo Cluster Galaxies and their Scaling Relations

By virtue of its proximity and richness, the Virgo galaxy cluster is a perfect testing ground to expand our understanding of structure formation in the Universe. Here, we present a comprehensive dynamical catalogue based on 190 Virgo cluster galaxies (VCGs) in the "Spectroscopy and H-band Imaging of the Virgo cluster" (SHIVir) survey, including kinematics and dynamical masses. Spectroscopy collected over a multi-year campaign on 4-8m telescopes was joined with optical and near-infrared imaging to create a cosmologically-representative overview of parameter distributions and scaling relations describing galaxy evolution in a rich cluster environment. The use of long-slit spectroscopy has allowed the extraction and systematic analysis of resolved kinematic profiles: Halpha rotation curves for late-type galaxies (LTGs), and velocity dispersion profiles for early-type galaxies (ETGs). The latter are shown to span a wide range of profile shapes which correlate with structural, morphological, and photometric parameters. A study of the distributions of surface brightnesses and circular velocities for ETGs and LTGs considered separately show them all to be strongly bimodal, hinting at the existence of dynamically unstable modes where the baryon and dark matter fractions may be comparable within the inner regions of galaxies. Both our Tully-Fisher relation for LTGs and Fundamental Plane analysis for ETGs exhibit the smallest scatter when a velocity metric probing the galaxy at larger radii (where the baryonic fraction becomes sub-dominant) is used: rotational velocity measured in the outer disc at the 23.5 i-mag arcsec^{-2} level, and velocity dispersion measured within an aperture of 2 effective radii, respectively. Dynamical estimates for gas-poor and gas-rich VCGs are merged into a joint analysis of the stellar-to-total mass relation (STMR), stellar TFR, and Mass-Size relation. These relations are all found to contain strong bimodalities or dichotomies between the ETG and LTG samples, alluding to a "mixed scenario'' evolutionary sequence between morphological/dynamical classes that involves both quenching and dry mergers. The unmistakable differentiation between these two galaxy classes appears robust against different classification schemes, and supports the notion that they are driven by different evolutionary histories. Future observations using integral field spectroscopy and including lower-mass galaxies should solidify this hypothesis.

Near-infrared polarimetry in the galactic center. On properties of Sagittarius A* and a dusty S-cluster object

Near-infrared polarimetry observation is a powerful tool to study the central sources at the center of the Milky Way. My aim of this thesis is to analyze the polarized emission present in the central few light years of the Galactic Center region, in particular the non-thermal polarized emission of Sagittarius~A* (Sgr~A*), the electromagnetic manifestation of the super-massive black hole, and the polarized emission of an infrared-excess source in the literature referred to as DSO/G2. This source is in orbit about Sgr~A*. In this thesis I focus onto the Galactic Center observations at $\lambda=2.2~\mu m$ ($K_\mathrm{s}$-band) in polarimetry mode during several epochs from 2004 to 2012. The near-infrared polarized observations have been carried out using the adaptive optics instrument NAOS/CONICA and Wollaston prism at the Very Large Telescope of ESO (European Southern Observatory). Linear polarization at 2.2 $\mu m$, its flux statistics and time variation, can be used to constrain the physical conditions of the accretion process onto the central super-massive black hole. I present a statistical analysis of polarized $K_\mathrm{s}$-band emission from Sgr~A* and investigate the most comprehensive sample of near-infrared polarimetric light curves of this source up to now. I find several polarized flux excursions during the years and obtain an exponent of about 4 for the power-law fitted to polarized flux density distribution of fluxes above 5~mJy. Therefore, this distribution is closely linked to the single state power-law distribution of the total $K_\mathrm{s}$-band flux densities reported earlier by us. I find polarization degrees of the order of 20\%$\pm$10\% and a preferred polarization angle of $13^o\pm15^o$. Based on simulations of polarimetric measurements given the observed flux density and its uncertainty in orthogonal polarimetry channels, I find that the uncertainties of polarization parameters under a total flux density of $\sim 2\,{\mathrm{mJy}}$ are probably dominated by observational uncertainties. At higher flux densities there are intrinsic variations of polarization degree and angle within rather well constrained ranges. Since the emission is most likely due to optically thin synchrotron radiation, the obtained preferred polarization angle is very likely reflecting the intrinsic orientation of the Sgr~A* system i.e. an accretion disk or jet/wind scenario coupled to the super-massive black hole. Our polarization statistics show that Sgr~A* must be a stable system, both in terms of geometry, and the accretion process. I also investigate an infrared-excess source called G2 or Dusty S-cluster Object (DSO) moving on a highly eccentric orbit around the Galaxy's central black hole, Sgr~A*. I use for the first time the near-infrared polarimetric imaging data to determine the nature and the properties of DSO and obtain an improved $K_\mathrm{s}$-band identification of this source in median polarimetry images of different observing years. The source starts to deviate from the stellar confusion in 2008 data and it does not show a flux density variability based on our data set. Furthermore, I measure the polarization degree and angle of this source and conclude based on the simulations on polarization parameters that it is an intrinsically polarized source with a varying polarization angle as it approaches Sgr~A* position. I use the interpretation of the DSO polarimetry measurements to assess its possible properties.