2,692 research outputs found

    Optical Spectroscopy of 3d and 4d correlated electron systems.

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    In the context of this work, three different materials are studied via optical spec- troscopy methods. The three materials are La2Cu2O5, Fe3O4, and Ca2RuO4, where the first one is investigated via Fourier spectroscopy, while the latter two are stud- ied via spectroscopic ellipsometry

    First-principles calculations of anharmonic phonons in diamond and silicon at high temperature and pressure

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    Many ab initio approaches for calculating anharmonic phonon dispersion relations have recently been developed, taking advantage of improvements in computational power. In this thesis, anharmonic phonons in the diamond-type semiconductors silicon and diamond are studied using two of these recently developed ab initio techniques to better understand the role of anharmonicity in these materials at elevated temperatures and pressures. The two techniques are the self-consistent phonon method as implemented in the alamode code and the temperature dependent effective potential approach implemented in the TDEP code. Both these approaches rely on density functional theory calculations to compute anharmonic phonon frequencies from first principles. The renormalisation of the zone-centre optical phonon of silicon is calculated using both methods. The TDEP approach accurately reproduces the experimentally observed temperature dependence of the zone-centre phonon, whereas alamode underestimates the renormalisation. This underestimation is determined to originate from the exclusion of certain phonon–phonon interaction processes in a series expansion central to the self-consistent phonon method. In particular, an interaction process involving three phonons is identified to contribute strongly to the anharmonic phonon renormalisation. An attempt was made to extend alamode to include this interaction, which was, regrettably, unsuccessful. The TDEP approach is then applied to diamond in the same manner as silicon. The zone-centre optical phonon is calculated and a comparison to available experimental data is made. The approach is again found to accurately reproduce the experimental data. Consequently, the TDEP approach is used to investigate the so-called quantum isotope effect in diamond. Deviations from the harmonic frequency ratio of the zone-centre phonons are used to investigate the anharmonic nature of the interatomic potential, as well as to search for an experimentally suggested “inversion” of the quantum isotope effect at high pressure. No such inversion of the quantum isotope effect is observed in the calculations made here. A detailed comparison of the effect of different exchange–correlation functionals and pseudopotentials on the density functional theory calculations is made, ultimately recommending local density approximation as the most accurate predictor of phonon frequencies in diamond. Finally, the Raman frequency of natural diamond is calculated at high temperature and pressure using the highly accurate TDEP method. Improvements are made to the stochastic sampling process, eliminating unwanted scatter from misaligned eigenvectors at degenerate points in the Brillouin zone and increasing the precision of the method. The calculated Raman frequency is used to suggest a calibration of the high-frequency edge of the Raman signal from a diamond anvil, which is used as a pressure marker in very-high-pressure experiments. The suggested calibration extends to pressures up to 1 TPa and temperatures up to 2000 K

    Crystal Structures of Metal Complexes

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    This reprint contains 11 papers published in a Special Issue of Molecules entitled "Crystal Structures of Metal Complexes". I will be very happy if readers will be interested in the crystal structures of metal complexes

    Hydrogen-bonding receptors for anion recovery in a capacitive deionisation system

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    Receptors are ubiquitous throughout nature and are found heavily within biological systems. This has led to synthetic supramolecular chemists to modify or develop analogous mimics of these receptors with high affinity and specificity for a range of target compounds, for potential commercial use. One group of particular interest are receptors that function through the formation of hydrogen bonds to the guest species. This class of receptor has been shown to have a range of different structural geometries and binding motifs, that allow for the sequestration of a number of different species. In the context of this work, anionic hydrogen-bonding receptors, specifically for ‘phosphate’- in most cases dihydrogenphosphate- and bicarbonate are of interest. Phosphate is an integral part of the DNA backbone, however a organophosphorus containing compounds also comprise a large group of chemical weapons which can have a devasting impact on the bodies ability to function. Chemical weapon compounds, such as sarin and Novichok, are based on the functionalisation of a central phosphate core which can be biotransformed into a highly potent active species within the body. Phosphate is also an essential component of plant fertilizers and is used on a huge scale in order to maintain global food security. However, phosphate loss as a consequence of agricultural run-off leads to reduced availability of essential minerals as well as large scale eutrophication. One such method that could be utilised for the recovery of phosphate is electrochemical capacitive deionisation. The principle and idea of capacitive deionisation has been around since the late 1960’s to early 1970’s and has been shown to be a suitable method for the desalination of low-to-medium salinity input streams. The purpose of the work within this thesis was to modify and synthesise receptors that could be covalently attached to porous carbon electrodes and impart selectivity to a capacitive deionisation system. In Chapter 1, the importance of ‘phosphate’, biologically and commercially is addressed before an in depth look at some of the phosphate specific hydrogen bonding receptors that have been reported in the literature. The design of a successful hydrogen bonding receptor relies on the correct orientation of the binding motifs and the range of structural scaffolds have been shown to be useable. Following this, the electrochemical principles of capacitive deionisation and its suitability for the recovery of phosphate are detailed, including some examples of capacitive deionisation set-ups and the overall processes involved. Chapter 2 details the theory of the techniques used throughout this thesis, which include, but not limited to, 1H and 13C NMR for the structural elucidation of the synthesised receptors and cyclic voltammetry which was used for the attachment of organic groups to an electrode. The historical and theoretical background established in Chapters 1 and 2 will lead into the work undertaken in Chapters 3-5. Chapter 3 focusses on the first of three hydrogen bonding receptors synthesised. Building upon previous work within the field, two neutral indole-based receptors were modified to include two different potential attachment points for the electrode- a carboxylic acid and an alkyne. Following the successful synthesis of the alkyne-based receptor, 1H NMR titrations were used to confirm the affinity of the new receptor for dihydrogenphosphate. Chapter 4 introduces the second anion of interest, bicarbonate. The underlying principles for hydrogen bonding are the same for bicarbonate, as in phosphate, however a different receptor was synthesised. The carbazole receptor synthesised contained free amine groups that were proposed to act as points of attachment to an already surface bound organic spacer group. 1H NMR titrations are once again used to determine the affinity of the receptor for the bicarbonate anion. Finally, Chapter 5 introduces the second of the dihydrogenphosphate-specific receptors, this time based on the amino acid leucine. UVVis titrations with a number of different anions were used to determine the affinity of the receptor. Within this chapter, methods for the attachment of organic groups are detailed including the electroreduction of 4-nitrobenzene diazonium and the direct oxidation of the alkyne

    Implicit Transfer Operator Learning: Multiple Time-Resolution Surrogates for Molecular Dynamics

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    Computing properties of molecular systems rely on estimating expectations of the (unnormalized) Boltzmann distribution. Molecular dynamics (MD) is a broadly adopted technique to approximate such quantities. However, stable simulations rely on very small integration time-steps (1015s10^{-15}\,\mathrm{s}), whereas convergence of some moments, e.g. binding free energy or rates, might rely on sampling processes on time-scales as long as 101s10^{-1}\, \mathrm{s}, and these simulations must be repeated for every molecular system independently. Here, we present Implict Transfer Operator (ITO) Learning, a framework to learn surrogates of the simulation process with multiple time-resolutions. We implement ITO with denoising diffusion probabilistic models with a new SE(3) equivariant architecture and show the resulting models can generate self-consistent stochastic dynamics across multiple time-scales, even when the system is only partially observed. Finally, we present a coarse-grained CG-SE3-ITO model which can quantitatively model all-atom molecular dynamics using only coarse molecular representations. As such, ITO provides an important step towards multiple time- and space-resolution acceleration of MD.Comment: 21 pages, 10 figure

    Understanding Gas and Energy Storage in Geological Formations with Molecular Simulations

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    Methane (CH4), the cleanest burning fossil fuel, has the potential to solve the energy crisis owing to the growing population and geopolitical tensions. Whilst highly calorific, realising its potential requires efficient storage solutions, which are safe and less energy-intensive during production and transportation. On the other hand, carbon dioxide (CO2), the by-product of human activities, exacerbates global heating driving climate change. CH4 is abundant in natural systems, in the form of gas hydrate and trapped gas within geological formations. The primary aim of this project was to learn how Nature could store such a large quantity of CH4 and how we can potentially extract and replace the in-place CH4 with atmospheric CO2, thereby reducing greenhouse gas emissions. We studied this question by applying molecular dynamics (MD) and Monte Carlo (MC) simulation techniques. Such techniques allow us to understand the behaviour of confined fluids, i.e., within the micropores of silica and kerogen matrices. Our simulations showed that CH4 hydrate in confinement could form under milder conditions than required, deviating from the typical methane-water phase diagram, complementing experimental observations. This research can contribute to artificial gas hydrate production via porous materials for gas storage. Besides that, the creation of 3D kerogen models via simulated annealing has enabled us to understand how maturity level affects the structural heterogeneity of the matrices and, ultimately CH4 diffusion. Immature and overmature kerogen types were identified to having fast CH4 diffusion. Subsequently, our proof-of-concept study demonstrated the feasibility of recovering CH4 via supercritical CO2 injection into kerogens. Insights from our study also explained why full recovery of CH4 is impossible. A pseudo-second-order rate law can predict the kinetics of such a process and the replacement quantity. A higher CO2 input required than the CH4 recovered highlights the possibility of achieving a net-zero future via geological CO2 sequestration

    AB-INITIO INVESTIGATION OF 2D MATERIALS FOR GAS SENSING, ENERGY STORAGE AND SPINTRONIC APPLICATIONS

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    The field of Two Dimensional (2D) materials has been extensively studied since their discovery in 2004, owing to their remarkable combination of properties. My thesis focuses on exploring novel 2D materials such as Graphene Nanoribbon (GNR), holey carbon nitride C2N, and MXenes for energy storage, gas sensing, and spintronic applications, utilizing state-of-the-art techniques that combine Density Functional Theory (DFT) and Non-Equilibrium Greens Functions (NEGF) formalism; namely Vienna Ab-initio Simulation Package (VASP) and Atomistic Toolkit (ATK) package.Firstly, on the side of gas sensing, the burning of fossil fuels raises the level of toxic gas and contributes to global warming, necessitating the development of highly sensitive gas sensors. To start with, the adsorption and gas-sensing properties of bilaterally edge doped (B/N) GNRs were investigated. The transport properties revealed that the bilateral B/N edge-doping of GNR yielded Negative Differential Resistance (NDR) IV-characteristics, due to the electron back-scattering which was beneficial for selective gas sensing applications. Therefore, both GNR: B/N were found to be good sensors for NO2 and SO3 respectively. After that, the catalytic activity of four magnetic transition metal “TM” elements (e.g., Mn, Fe, Co and Ni) embedded in C2N pores, as Single-Atom Catalysts (SAC), was tested towards detecting toxic oxidizing gases. The results of spin-polarized transport properties revealed that Ni- and Fe-embedded C2N are the most efficient in detecting NO/ NO2 and NO2 molecules.Secondly, on the side of energy storage, since the fossil fuels reserves are depleting at an alarming rate, there is an urgent need for alternative forms of energy to meet the ever-growing demand for energy. Hydrogen is a popular form of clean energy. However, its storage and handling are challenging because of its explosive nature. The effect of magnetic moment on the hydrogen adsorption and gas-sensing properties in Mn-embedded in C2N were investigated. Two distinct configurations of embedment were considered: (i) SAC: 1Mn@C2N; and (ii) DAC: Mn2@C2N. Based on the huge changes in electronic and magnetic properties and the low recovery time (i.e., τ ≪ 1 s, τ = 92 μs and 1.8 ms, respectively), we concluded that C2N:Mn is an excellent candidate for (reusable) hydrogen magnetic gas sensor with high sensitivity and selectivity and rapid recovery time. Then, a comparative study of hydrogen storage capabilities on Metal- catalyst embedded (Ca versus Mn) C2N is presented which demonstrated the stability of these metal structures embedded on the C2N substrate. We proposed Ca@C2N and Mn@C2N for dual applications- hydrogen storage and a novel electrode for prospective metal-ion battery applications owing to its high irreversible uptake capacity 200 mAhg-1.Thirdly, on the side of data storage, spintronics is an emerging field for the next generation nanoelectronics devices to reduce their power consumption and to increase their memory and processing capabilities. Designing 2D-materials that exhibit half-metallic properties is important in spintronic devices that are used in low-power high-density logic circuits. We tested samples comprising of SAC and DAC of Mn embedded in a C2N sample size 2×2 primitive cells as well as their combinations in neighboring large pores. Many other TM catalysts were screened, and the results show the existence of half metallicity in just five cases: (a) C2N:Mn (DAC, SAC-SAC, and SAC-DAC); (b) C2N:Fe (DAC); and (c) C2N:Ni (SAC-DAC). Our results further showed the origins of half-metallicity to be attributed to both FMC and synergetic interactions between the catalysts with the six mirror images, formed by the periodic-boundary conditions.Lastly, on the side of batteries, sodium-sulfur batteries show great potential for storing large amounts of energy due to their ability to undergo a double electron- redox process, as well as the plentiful abundance of sodium and sulfur resources. However, the shuttle effect caused by intermediate sodium polysulfides (Na2Sn) limits their performance and lifespan. To address this issue, we proposed two functionalized MXenes Hf3C2T2 and Zr3C2T2 (T= F, O), as cathode additives to suppress the shuttle effect. We found that both Hf3C2T2 and Zr3C2T2 systems inhibit the shuttle effect by binding to Na2Sn with a binding energy higher than the electrolyte solvents. The decomposition barrier for Na2Sn on the O functionalized MXenes gets reduced which enhances the electrochemical process. Overall, our findings show that the tuning of 2D materials can lead to promising applications in various fields, including energy storage, gas sensing, and spintronics

    Luminescent Nanocrystals: Line broadening and formation mechanisms

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    Nanomaterials have become an increasingly important class of materials in the past decades due to their size-tunable optical, electronic, and magnetic properties. Nanomaterials are not only of great scientific interest, but their versatility has also resulted in a wide range of applica¬tions. This thesis focuses on two types of luminescent (light-emitting) nanomaterials, cadmium chalcogenide nanocrystals (NCs) and NaYF4 NCs doped with rare earth ions (lanthanides, e.g., erbium and ytterbium). Both the optical properties and nanocrystal growth mechanisms are investigated. Semiconductor NCs, especially CdSe nanoplatelets (NPLs), exhibit narrow emission bands in the visible part of the spectrum, a property needed for more efficient white light LEDs (w-LEDs) and vibrant displays. In these applications, the luminescent materials operate at elevated tem¬peratures, which affects the emission linewidth. Insight into this thermal broadening is important for application in w-LEDs but has so far not been investigated over a temperature range that is relevant for these applications. In this thesis, I report on the temperature-dependent spectral linewidth of cadmium chalcogenide NPLs and QDs. NaYF4 NCs doped with lanthanide ions are efficient upconversion materials that can convert two low-energy infrared photons to one high-energy visible photon. These materials can be used in deep-tissue imaging and to enhance the efficiency of solar cells. The formation mechanism of both NaYF4 NCs and CdSe NPLs is still debated. Control over the NC growth is essential to adjust the NC properties. In this thesis, I report on the mechanisms of their nucleation and growth, monitored using in situ absorption and x-ray scattering techniques

    Enhancing the Structural Stability of α-phase Hybrid Perovskite Films through Defect Engineering Approaches under Ambient Conditions

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    This thesis investigates methods whereby perovskite solar cell power conversion efficiency and material stability may be improved. Hybrid perovskites have gained increased attention for optoelectronic applications due to favourable properties such as strong absorption, facile processing, and changeable band-gap. Despite excellent improvements in power conversion efficiency of devices, perovskite films are unstable, degrading with relative ease in the presence of moisture, oxygen, light, heat, and electric fields. The focus of this thesis is on ambient atmosphere stability, concerned with the influence of moisture in particular on perovskite film fabrication, degradation, and device functionality. In order to shed light on the impact of ambient atmosphere on perovskite films, experiments are designed to investigate films during fabrication and degradation. The influences firstly of stoichiometry during ambient fabrication, and then ionic substitution (with caesium and formadinium) upon moisture-induced degradation are investigated. Finally, films and devices with a novel composition incorporating Zn are fabricated under ambient conditions to investigate the effect of Zn addition on perovskite film stability

    Beam scanning by liquid-crystal biasing in a modified SIW structure

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    A fixed-frequency beam-scanning 1D antenna based on Liquid Crystals (LCs) is designed for application in 2D scanning with lateral alignment. The 2D array environment imposes full decoupling of adjacent 1D antennas, which often conflicts with the LC requirement of DC biasing: the proposed design accommodates both. The LC medium is placed inside a Substrate Integrated Waveguide (SIW) modified to work as a Groove Gap Waveguide, with radiating slots etched on the upper broad wall, that radiates as a Leaky-Wave Antenna (LWA). This allows effective application of the DC bias voltage needed for tuning the LCs. At the same time, the RF field remains laterally confined, enabling the possibility to lay several antennas in parallel and achieve 2D beam scanning. The design is validated by simulation employing the actual properties of a commercial LC medium
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