Tesis sobre el tema "Metal density"
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1
Hamilton, Craig D. "Density functional calculations of organometallic complexes containing metal-metal multiple bonds /". The Ohio State University, 1998. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487950153600457.
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McAllister, B. P. "A density functional theory study of reactions of metal and metal oxides". Thesis, Queen's University Belfast, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.426760.
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Louca, P. "From X-ray structure factors to electron-density distributions". Thesis, University of Bristol, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.374638.
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Remenyi, Christian. "Density functional studies on EPR parameters and spin-density distributions of transition metal complexes". Doctoral thesis, [S.l.] : [s.n.], 2006. http://deposit.ddb.de/cgi-bin/dokserv?idn=982187890.
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Ravetz, Megan Sarah. "Effect metal electron density on C-H activation reactions". Thesis, University of Salford, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.360458.
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Burrill, Daniel. "Density Functional Theory Study of Dilute Transition Metal Phthalocyanines". ScholarWorks @ UVM, 2015. http://scholarworks.uvm.edu/graddis/508.
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Organometallic (OM) crystals are studied in fields ranging from spintronics to photovoltaics. This thesis focuses on studying a particular class of OM crystals known as transition metal-phthalocyanines (TM-Pc) - a molecular crystal composed of chains of planar OM molecules with a transition metal center and four coordinated pyrrole-aromatic rings joined by nitrogen atoms, similar to porphyrin. The structure resembles a dish rack pattern where the planar TM-Pcs of adjacent chains are oriented nearly perpendicular to each other. While TM-Pcs have been studied for decades due to their interesting optical properties and applications as dyes, there has been recent interest in understanding the magnetic properties with various transition metals.
Due to crystal arrangement, inter-chain interactions among TM-Pcs are relatively weak when compared to intra-chain interactions. This property allows the chains of TM-Pcs to be isolated and approximated as a pseudo 1D system. The electronic structure and spin exchange are computationally examined along chains of CuPc when they have been diluted with the metal-free variant, H2Pc. Density functional theory is employed with the Hubbard U correction to account for electron interactions on the copper d-orbitals. Since the diluted systems are effectively 1D with narrow bands along their stacking axis, a 1D Heisenberg model is applied where the exchange coefficient is determined through the Broken Symmetry method. Additionally, the effect of non-local corrections, used to determine structural features, on the Hubbard U and Heisenberg exchange coefficient, J, are discussed.
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Zhuang, Houlong. "First-principles studies of metal-carbon nanotube systems". Click to view the E-thesis via HKUTO, 2007. http://sunzi.lib.hku.hk/hkuto/record/B39395789.
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Zhuang, Houlong y 庄厚龍. "First-principles studies of metal-carbon nanotube systems". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2007. http://hub.hku.hk/bib/B39395789.
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Wang, Jiaqi. "Transition Metal Catalyzed Oxidative Cleavage of C-O Bond". Thesis, University of North Texas, 2015. https://digital.library.unt.edu/ark:/67531/metadc801914/.
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The focus of this thesis is on C-O bonds activation by transition metal atoms. Lignin is a potential alternative energy resource, but currently is an underused biomass species because of its highly branched structure. To aid in better understanding this species, the oxidative cleavage of the Cβ-O bond in an archetypal arylglycerol β-aryl ether (β–O–4 Linkage) model compound of lignin with late 3d, 4d, and 5d metals was investigated. Methoxyethane was utilized as a model molecule to study the activation of the C-O bond. Binding enthalpies (ΔHb), enthalpy formations (ΔH) and activation enthalpies (ΔH‡) have been studied at 298K to learn the energetic properties in the C-O bond cleavage in methoxyethane. Density functional theory (DFT) has become a common choice for the transition metal containing systems. It is important to select suitable functionals for the target reactions, especially for systems with degeneracies that lead to static correlation effects. A set of 26 density functionals including eight GGA, six meta-GGA, six hybrid-GGA, and six hybrid-meta-GGA were applied in order to investigate the performance of different types of density functionals for transition metal catalyzed C-O bond cleavage. A CR-CCSD(T)/aug-cc-pVTZ was used to calibrate the performance of different density functionals.
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Bansal, Shubhra. "Characterization of Nanostructured Metals and Metal Nanowires for Ultra-High Density Chip-to-Package Interconnections". Diss., Georgia Institute of Technology, 2006. http://hdl.handle.net/1853/14041.
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Nanocrystalline materials are being explored as potential off-chip interconnects materials for next generation microelectronics packaging. Mechanical behavior and deformation mechanisms in nanocrystalline copper and nickel have been explored. Nanostructured copper interconnections exhibit better fatigue life as compared to microcrystalline copper interconnects at a pitch of 100 and #956;m and lower. Nanocrystalline copper is quite stable upto 100 oC whereas nickel is stable even up to 400 oC. Grain boundary (GB) diffusion along with grain rotation and coalescence has been identified as the grain growth mechanism. Ultimate tensile and yield strength of nanocrystalline (nc) Cu and Ni are atleast 5 times higher than microcrystalline counterparts. Considerable amount of plastic deformation has been observed and the fracture is ductile in nature. Fracture surfaces show dimples much larger than grain size and stretching between dimples indicates localized plastic deformation. Activation energies for creep are close to GB diffusion activation energies indicating GB diffusion creep. Creep rupture at 45o to the loading axis and fracture surface shows lot of voiding and ductile kind of fracture. Grain rotation and coalescence along direction of maximum resolved shear stress plays an important role during creep. Grain refinement enhances the endurance limit and hence high cycle fatigue life. However, a deteriorating effect of grain refinement has been observed on low cycle fatigue life. This is because of the ease of crack initiation in nanomaterials. Persistent slip bands (PSBs) at an angle of 45o to loading axis are observed at higher strain ranges (> 1% for nc- Cu) with a width of about 50 nm. No relationship has been observed between PSBs and crack initiation. A non-recrystallization annealing treatment, 100 oC/ 2 hrs for nc- Cu and 250 oC/ 2 hrs for nc- Ni has been shown to improve the LCF life without lowering the strength much. Fatigue crack growth resistance is higher in nc- Cu and Ni compared to their microcrystalline counterparts. This is due to crack deflection at GBs leading to a tortuous crack path. Nanomaterials exhibit higher threshold stress intensity factors and effective threshold stress intensity is proportional to the elastic modulus of the material.
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Durr, Christopher Blair. "The Effect of Metal Containing Ligands on The Metal-Metal Quadruple Bond: Structure, Synthesis, And Photophysics". The Ohio State University, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=osu1429542171.
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Sadjadi, Seyedabdolreza. "Ab initio relativistic-consistent calculations and charge density and experimental mass-spectroscopic analysis of mono and poly-nuclearclusters of group 11 and 12 transition metals and metal chlorides: ySeyedabdolreza Sadjadi". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2013. http://hub.hku.hk/bib/B5060577X.
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The electron density function of molecular systems supplies a package of information. Quantum mechanical methods of producing and analyzing this function have been significantly improved during the past few years. The advent of accurate pseudopotentials and corresponding basis sets for Kohn-Sham density functional and for post-Hartree-Fock electron-correlated approaches have enabled the inclusion of scalar relativistic and spin-orbit coupling effects as well as electron correlation effects into the electron density function. The unpacking of the information embedded in such a function via the quantum theory of atoms in molecules (QTAIM) became possible by utilizing the very new subshell fitting method of reconstructing the density distribution of core electrons that had been replaced by the pseudopotentials.
These theoretical advances were applied in this thesis to characterize and explore the topological features of metal-metal bonding as one of the fundamental types of bonds formed between two elements. Group 11 and 12 transition metals which include gold and mercury as the most relativistic elements were the main focus of this work. Mono and poly-nuclear compounds (with up to 4 metal atoms) in both pure metal clusters and chloro-complexes were studied by ab initio MØller-Plesset perturbation calculations followed by QTAIM analysis on the relaxed density. Some of these chloro-complexes of copper, gold, zinc and cadmium metals were identified in the gas phase by mass spectrometric experiments. The general formulas of the set of molecules studied in group 11 were : M2, MCl, MCl+, MCl2, MCl2+, M2Cl+, M2Cl2^(s+), M2Cl3+, M3Cl2+, M3Cl3+, M3Cl5+, M4Cl5+ and M4Cl7+ and in group 12 were : M2, MCl, MCl+, MCl2, M2Cl3+, M3Cl5+, M4Cl7+ and M2^(s+). The topological features of metal-metal bonding were calculated along with atomic properties for each individual local minimum isomer found. The comparison of
the metal-metal bonding within the complexes and with the dimers revealed new
features of metal-metal bonding in 3d, 4d and 5d transition metal elements of
groups 11 and 12. With the aid of strong correlation between bond dissociation
energy and electron density at the location of the bond critical points found in the
case of dimers, the strength of the metal-metal bonding in the complexes was
estimated. The electron density’s basin properties calculated accurately for all the
clusters and their isomers in this thesis provided more insight also into the nature
of M-Cl bondings in the group 11 and 12 chloride clusters. Ultimately the bonding
information was used to predict the viability of these clusters in the gas phase.published_or_final_version
Chemistry
Doctoral
Doctor of Philosophy
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Durivage, Jason Curtis. "Ligand Effects on Metal-Metal Bonding: Photoelectron Spectroscopy and Electronic Structure Calculations of Dimetal Paddlewheel Complexes". Diss., The University of Arizona, 2011. http://hdl.handle.net/10150/145427.
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Paddlewheel complexes are molecules in which two interacting metal atoms are bridged by four chelating ligands. This class of complexes has a large range of electronic variability while keeping a rigid geometric structure. This variability has led to their use as catalysts, strong reductants, anti-tumor agents, and electron transfer agents. This dissertation examines the effects of changing both the dimetal core and the surrounding ligands on the electronic structure properties of the paddlewheel complexes. Examination of Bi₂(O₂CCF₃)₄, a p-orbital dimetal paddlewheel complex, provided a way to probe the orbitals that are important in metal-ligand σ bonding. The b(1g) and b(2u) ligand orbitals of Bi₂(O₂CCF₃)₄ have no dimetal orbital counterpart, unlike the case of the more familiar d-orbital dimetal paddlewheel complexes such as Mo₂(O₂CCF₃)₄. This had the effect of destabilizing these ligand orbitals compared to d-orbital paddlewheel complexes. The ligand a1g orbital in Bi₂(O₂CCF₃)₄ was also destabilized due to nodal differences in the dimetal σ orbital. The unusual coincidence of Mo-Mo σ and π ionization bands is due to a greater amount of ligand character in the Mo-Mo σ orbital compared to its ditungsten analogue, which has separate ionization bands for the σ and π bonds. A series of p-substituted dimolybdenum tetrabenzoate complexes was synthesized and studied by photoelectron spectroscopy in order to further examine the delocalization of electron density from the metals to the ligands in these complexes. A 0.89 eV shift in the δ ionization band was observed from Mo₂(O₂CPh-p-OMe) ₄ and Mo₂(O₂CPh-p-CF₃)₄. Overlap effects are the major factor causing the shift in the δ bond ionization, as the calculated charges on the molybdenum and oxygen atoms did not vary significantly on change of substituent. Molybdenum and tungsten guanidinate paddlewheel complexes have promise as good reducing agents due to their extremely low ionization energies. The solubility of the complexes poses a problem for their widespread adoption for use as reducing agents. Alkyl substituents were added to the complexes to increase their solubility. W₂(TEhpp)₄ was observed to have the lowest ionization energy at 3.71 eV (vertical ionization) and 3.40 eV (onset ionization) of any molecule yet prepared.
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Dang, Li. "Density functional theory studies of copper(I) mediated borylation and carboxylation reactions /". View abstract or full-text, 2010. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202010%20DANG.
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Crabtree, Elaine. "The role of metal ions in LDL peroxidation". Thesis, Birkbeck (University of London), 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.266211.
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Wang, Jiaqi. "The Impact of Computational Methods on Transition Metal-containing Species". Thesis, University of North Texas, 2015. https://digital.library.unt.edu/ark:/67531/metadc822795/.
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Quantum chemistry methodologies can be used to address a wide variety of chemical problems. Key to the success of quantum chemistry methodologies, however, is the selection of suitable methodologies for specific problems of interest, which often requires significant assessment. To gauge a number of methodologies, the utility of density functionals (BLYP, B97D, TPSS, M06L, PBE0, B3LYP, M06, and TPSSh) in predicting reaction energetics was examined for model studies of C-O bond activation of methoxyethane and methanol. These species provide excellent representative examples of lignin degradation via C-O bond cleavage. PBE0, which performed better than other considered DFT functionals, was used to investigate late 3d (Fe, Co, and Ni), 4d (Ru, Rh, and Pd), and 5d (Re, Os, and Ir) transition metal atom mediated Cβ -O bond activation of the β–O–4 linkage of lignin. Additionally, the impact of the choice of DFT functionals, basis sets, implicit solvation models, and layered quantum chemical methods (i.e., ONIOM, Our Own N-layered Integrated molecular Orbital and molecular Mechanics) was investigated for the prediction of pKa for a set of Ni-group metal hydrides (M = Ni, Pd, and Pt) in acetonitrile. These investigations have provided insight about the utility of a number of theoretical methods in the computation of thermodynamic properties of transition metal hydrides in solution. As single reference wavefunction methods commonly perform poorly in describing molecular systems that involve bond-breaking and forming or electronic near-degeneracies and are typically best described with computationally costly multireference wavefunction-based methods, it is imperative to a priori analyze the multireference character for molecular systems so that the proper methodology choice is applied. In this work, diagnostic criteria for assessing the multireference character of 4d transition metal-containing molecules was investigated. Four diagnostics were considered in this work, including the weight of the leading configuration of the CASSCF wavefunction, C02; T1, the Frobenius norm of the coupled cluster amplitude vector related to single excitations and D1, the matrix norm of the coupled cluster amplitude vector arising from coupled cluster calculations; and the percent total atomization energy, %TAE. This work demonstrated the need to have different diagnostic criteria for 4d molecules than for main group molecules.
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Tang, Miru. "DENSITY FUNCTIONAL THEORY STUDIES ON THE STRUCTURE AND CATALYTIC ACTIVITY OF METAL OXIDES". OpenSIUC, 2018. https://opensiuc.lib.siu.edu/dissertations/1602.
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In this dissertation, I present four projects on the fundamental study of the surface configurations and reactivity of the metal oxides using density functional theory computational method. In the first project, we studied the formaldehyde adsorption and diffusion on rutile TiO2 (110) surface. By comparing the adsorption of formaldehyde on stoichiometric and defective TiO2 surfaces under the same condition, we evaluated the effect of surface oxygen vacancy on their interaction with formaldehyde. The project involved close collaboration with Dr. Zhenrong Zhang’s group of Baylor University who studied the formaldehyde chemistry on rutile TiO2(110) surface using a combination of STM and other surface science techniques. In the second project, we compared the surface chemistries of formaldehyde and formic acid on rutile TiO2 and SnO2, two structurally similar but chemically different oxides. We analyzed the oxidation of formaldehyde to formic acid on two oxides and assessed the role of surface oxygen in the oxidation. In the third project, we studied the oxygen evolution reaction (OER) catalyzed by γ-FeOOH (010) under the alkaline condition. The OER process was divided into four elementary steps and the potential energy profiles of these steps on three terminations of the γ-FeOOH (010) surface were mapped out. Based on the computed reaction energies, we determined the most probable OER reaction pathway on each surface termination. We found that partially exposed surface Fe sites were the active sites for the OER process. In the fourth project, we studied the potential of iron oxides (FeOx) and iron-titanium mixed oxides (FeTiOx) as solid oxygen carriers for the chemical looping combustion (CLC) process. As oxygen carriers for CLC, FeOx and FeTiOx in fully oxidized forms went through a series of reduction steps by reacting with the fuel molecules. The reduced oxides were then re-oxidized in an air reactor to restore their oxygen. By studying the surface oxygen vacancy formation and oxygen diffusion, we gained insights into the initial stage of reduction process and activities of FeOx and FeTiOx as well as the effect of Ti on oxygen carrying properties of FeTiOx for CLC.
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唐素明 y So-ming Glenna Tong. "Theoretical studies of transition metal containing diatomics and DNA electron transfer". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2002. http://hub.hku.hk/bib/B31244828.
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Schiros, Theanne. "Water-Metal Surfaces : Insights from core-level spectroscopy and density functional theory". Doctoral thesis, Stockholm University, Department of Physics, 2008. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-7435.
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Computational methods are combined with synchrotron-based techniques to analyze the structure and bonding of water and water plus hydroxyl at metal surfaces under UHV and at near-ambient conditions. Water-metal interaction plays a crucial role in a multitude of cosmic, atmospheric and biological phenomena as well as heterogeneous catalysis, electrochemistry and corrosion. A spotlight of renewed interest has recently been cast on water-metal systems due to their relevance for surface chemical reactions related to the production and utilization of hydrogen as a clean energy carrier. In particular, H2O and OH are essential reaction intermediates in the renewable production of hydrogen from sunlight and water and in fuel cell electrocatalysis.
Fuel cells are considered one of the most promising power generation technologies for a sustainable energy future. A mechanistic understanding of the oxygen reduction reaction (ORR) pathway, including the role of electronic and geometric structure of the catalyst, is essential to the design of more efficient fuel cell catalysts. This is intimately connected to fundamental factors that affect the ability to form water-metal bonds as well as the site occupation and orientation of the adsorbed H2O and OH at active metal surfaces.
Key relationships related to critical issues in the fuel cell reaction are illuminated by the synergy of theory and experiment in this thesis. We emerge with a detailed understanding of the structure of the water-metal interface and the factors that rule the wettability of a metal surface, including geometric and electronic structure effects and the influence of coadsorbed species. We show that the preferred microscopic orientation of the water monolayer has consequences for macroscopic properties, and reveal the origin of the hydrophobic water layer. Finally, we identify a cooperativity effect that drives the stability of the mixed water/hydroxyl layer at metal surfaces, an important ORR intermediate.
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Wedberg, Dan. "Dislocation density based material model applied in FE-simulation of metal cutting". Licentiate thesis, Luleå tekniska universitet, Material- och solidmekanik, 2010. http://urn.kb.se/resolve?urn=urn:nbn:se:ltu:diva-26278.
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Simulation based design enables rapid development of products with increased customer value in terms of accessibility, quality, productivity and profitability. However simulation of metal cutting is complex both in terms of numeric and physics. The work piece material undergoes severe deformations. The material model must therefore be able to accurately predict the deformation behavior for a large range of strain, strain rates (>50000 s-1) and temperatures. There exist a large number of different material models. They can be divided into empirical and physically based models. The far most common model used in simulation of metal cutting is the empirical Johnson-Cook plasticity model, JC model. Physically based models are based on the knowledge of the underlying physical phenomena and are expected to have larger domain of validity. Experimental measurements have been carried out in order to calibrate and validate a physical based material model utilizing dislocation density (DD) as internal variable. Split-Hopkinson tests have been performed in order to characterize the material behavior of SANMAC 316L at high strain rates. The DD model has been calibrated in earlier work by Lindgren et al. based on strain rate up to 10 s-1 and temperatures up to 1300 °C with good agreement over the range of calibration. Same good correspondence was not obtained when the model was extrapolated to high strain rate response curves from the dynamic Split-Hopkinson tests. These results indicate that new deformation mechanisms are entering. Repeating the calibration procedure for the empirical JC model shows that it can only describe the material behavior over a much more limited range. A recalibrated DD model, using varying obstacle strength at different temperatures, was used in simulation of machining. It was implemented in an implicit and an explicit finite element code.Simulation of orthogonal cutting has been performed with JC model and DD model using an updated Lagrangian formulation and an implicit time stepping logic. An isotropic hardening formulation was used in this case. The results showed that the cutting forces were slightly better predicted by the DD model. Largest error was 16 % compared to 20 % by the JC model. The predicted chip morphology was also better with the DD model but far from acceptable. Orthogonal cutting was simulated using an updated Lagrangian formulation with an explicit time integration scheme. In this case were two hardening rules tested, isotropic hardening and a mixed isotropic-kinematic hardening. The later showed an improvement regarding the feed force prediction. A deviation of less than 8% could be noticed except for the feed force at a cutting speed of 100 m/min. The time stepping procedure in combination with the mesh refinement seems to be able to capture the chip segmentation quite well without including damage evolution in the material model.Further works will mainly focus on improving the DD-model by introducing relevant physics for high strain rates.Godkänd; 2010; 20100809 (danwed); LICENTIATSEMINARIUM Ämnesområde: Materialmekanik/Material Mechanics Examinator: Professor Lars-Erik Lindgren, Luleå tekniska universitet Diskutant: Professor Bevis Hutchinson, Swerea KIMAB, Stockholm Tid: Torsdag den 23 september 2010 kl 10.00 Plats: E246, Luleå tekniska universitet
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Martin, Lara J. "Study on metal adhesion mechanisms in high density interconnect printed circuit boards". Thesis, Georgia Institute of Technology, 2000. http://hdl.handle.net/1853/19628.
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Lamb, David J. "The oxidation of low density lipoprotein by cells and transition metal ions". Thesis, University of Reading, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.358450.
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Eaglesham, D. J. "Charge density waves and their phase transitions in the transition metal chalcogenides". Thesis, University of Bristol, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375017.
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Pardue, Daniel B. "Computational Studies of C–H/C–C Manipulation Utilizing Transition Metal Complexes". Thesis, University of North Texas, 2015. https://digital.library.unt.edu/ark:/67531/metadc801892/.
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Density Functional Theory (DFT) is an effective tool for studying diverse metal systems. Presented herein are studies of a variety of metal systems, which can be applied to accomplish transformations that are currently difficult/impossible to achieve. The specific topics studied utilizing DFT include: 1) C–H bond activation via an Earth-abundant transition metal complex, 2) C–H bond deprotonation via an alkali metal superbase, 3) and amination/aziridination reactions utilizing a CuI reagent. Using DFT, the transformation to methanol (CH3OH) from methane (CH4) was examined. The transition metal systems studied for this transformation included a model FeII complex. This first-row transition metal is an economical, Earth-abundant metal. The ligand set for this transformation includes a carbonyl ligand in one set of complexes as well as a phosphite ligand in another. The 3d Fe metal shows the ability to convert alkyls/aryls to their oxidized counterpart in an energetically favorable manner. Also, “superbasic” alkali metal amides were investigated to perform C—H bond cleavage. Toluene was the substrate of interest with Cs chosen to be the metal of interest because of the highly electropositive nature of this alkali metal. These highly electrophilic Cs metal systems allow for very favorable C—H bond scission with a toluene substrate. Finally, the amination and aziridination of C–H and C=C bonds, respectively, by a CuI reagent was studied. The mechanism was investigated using DFT calculations. Presently, these mechanisms involving the use of coinage metals are debated. Our DFT simulations shed some insight into how these transformations occur and ultimately how they can be manipulated.
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Paget, Veronica J. "The modelling of transition metal centres using molecular mechanics and density functional theory". Thesis, University of Bath, 1996. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.320428.
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Kirichenko, E. y E. Belovol. "High-energy-density sugar biobattery". Thesis, Sumy State University, 2014. http://essuir.sumdu.edu.ua/handle/123456789/45213.
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The rapidly growing demand for powering portable electronic devices is driving the development of better batteries with features such as enhanced energy-storage densities, high levels of safety, biodegradability and small environmental footprints.
The lithium-ion battery is often the system of choice because it offers a high energy density, has a flexible and light-weight design and has a longer lifespan than comparable battery technologies. The widespread use of metal-catalysed batteries also raises many concerns, primarily related to safety, toxic metal pollution and the availability of costly, limited, irreplaceable or rare metal resources.
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Malliakas, Christos D. "Charge density waves and structural modulations in polytelluride compounds". Diss., Connect to online resource - MSU authorized users, 2007.
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Olaoye, Olufemi Opeyemi. "Density functional calculation of simple molecules". Thesis, Stellenbosch : Stellenbosch University, 2012. http://hdl.handle.net/10019.1/20345.
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Thesis (MSc)--Stellenbosch University, 2012.AFRIKAANSE OPSOMMING: Berekeninge met Density Functional Theory (DFT) is ’n nuttige tegniek om die dinamika van molekules op potensiële energievlakke te verstaan. Beginnende met ’n prototipe molekuul formaldimien, wat die kern vorm van die groter fotochromiese molekuul dithizonatophenyl kwik (DPM), word die modellering van die molekuul meer ingewikkeld tot laasgenoemde bestudeer kan word asook sy fotochromiese afgeleides wat vervanging van elektronryk en elektronarm radikale by orto, meta en para posisies van die phenyl ringe insluit. DFT berekeninge word met spektra van Absorpsiespektroskopie met UV en sigbare lig asook tyd opgeloste spektra, verkry dmv femtosekondespektroskopie, vergelyk. In pol^ere aprotiese, pol^ere protiese en nie-pol^ere oplosmiddels, isomeriseer die molekuul om die C=N dubbelbinding. Daar kan tussen die twee isomere onderskei word deur dat die een in oplossing in sy grondtoestand blou en die ander een oranje voorkom. Die isomerisering is’n fotogeinduseerde proses. Die optimering van die molekul^ere struktuur, absorpsiespektra, oplosmiddel-afhanklikheid, en potensiële energievlak metings van die molekuul word bestudeer. Die sterk/swak wisselwerking wat in pol^ere protiese/aprotiese oplosmiddels verskyn word geopenbaar deur die hoe/lae absorpsie van die sekond^ere bande van die molekules. Daar is gevind dat die absorpsiespektra van DPM bathochromies in oplosmiddels met hoë diëlektriese konstantes is. Vir die potensiële energievlak berekeninge van die grondtoestand word rigiede en ontspanne metodes gebruik waar laasgenoemde met gebroke simmetrie berekeninge verkry word. Van alle metodes wat vir berekeninge gebruik was, gee die B3LYP/CEP-31G metode die beste benadering aan eksperimentele data. Alle berekeninge word gedoen met twee bekende sagteware pakkette; Amsterdam Density Functional (ADF) en Gaussian, wat op twee verskillende DFT metodes gebaseer is.
ENGLISH ABSTRACT: Density functional theory is a useful computational tool in the understanding of molecular dynamics on potential energy surfaces. Starting with a prototype molecule formaldimine, the photochromic molecule dithizonatophenylmercury II (DPM) and a set of its photochromic derivatives, (involving substitutions of electron donating and electron withdrawing substituents at ortho, meta and para positions of the dithizonato phenyl rings), are studied through density functional calculation in comparison with steady state absorption spectra obtained from UV-Visible and femto second spectroscopy experiments. In polar aprotic, polar protic and non-polar solvents these molecules isomerise around C=N double bond chromophore, from orange electronic ground states to blue electronic ground states upon photo-excitation. We investigate the structural optimisations, the absorption spectra, the solvent dependence and the potential energy surface (PES) of these molecules. The strong (weak) interactions exhibited by the polar protic (aprotic) solvents used are revealed through high (low) absorbance in the secondary bands of these molecules. The absorption spectra of DPM are found to be bathochromic in solvents with high dielectric constants. For the ground state PES calculation we make use of rigid and relaxed methods, and the latter is obtained through broken symmetry calculation. Of all the methods used in calculation, B3LYP/CEP-31G method gives the best approximation to the experimental data. All calculations are done using the two renown software, Amsterdam Density Functional (ADF) and Gaussian, availing their different density functional methods.
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Zhang, Yuhan. "POLYMER ELECTROLYTES FOR HIGH CURRENT DENSITY LITHIUM STRIPPING/PLATING TEST". University of Akron / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=akron1555090752890092.
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Moynihan, Randall H. "The flow stability of linear low-density polyethlene at polymer and metal interfaces". Diss., This resource online, 1990. http://scholar.lib.vt.edu/theses/available/etd-07132007-143144/.
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Lynch, Mark Francis. "Chemical reactions of small molecules on metal surfaces : a density functional theory study". Thesis, Queen's University Belfast, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.314017.
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Elliott, J. D. "The application of linear-scaling Density Functional Theory to large metal oxide nanotubes". Thesis, University of Liverpool, 2016. http://livrepository.liverpool.ac.uk/3003340/.
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Hagiya, Toru. "Electronic Excitation and Density Response in Liquid Alkali Metals Studied by Inelastic X-ray Scattering". Kyoto University, 2020. http://hdl.handle.net/2433/253075.
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Ritschel, Tobias. "Electronic self-organization in layered transition metal dichalcogenides". Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2015. http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-188265.
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The interplay between different self-organized electronically ordered states and their relation to unconventional electronic properties like superconductivity constitutes one of the most exciting challenges of modern condensed matter physics. In the present thesis this issue is thoroughly investigated for the prototypical layered material 1T-TaS2 both experimentally and theoretically.
At first the static charge density wave order in 1T-TaS2 is investigated as a function of pressure and temperature by means of X-ray diffraction. These data indeed reveal that the superconductivity in this material coexists with an inhomogeneous charge density wave on a macroscopic scale in real space. This result is fundamentally different from a previously proposed separation of superconducting and insulating regions in real space. Furthermore, the X-ray diffraction data uncover the important role of interlayer correlations in 1T-TaS2.
Based on the detailed insights into the charge density wave structure obtained by the X-ray diffraction experiments, density functional theory models are deduced in order to describe the electronic structure of 1T-TaS2 in the second part of this thesis. As opposed to most previous studies, these calculations take the three-dimensional character of the charge density wave into account. Indeed the electronic structure calculations uncover complex orbital textures, which are interwoven with the charge density wave order and cause dramatic differences in the electronic structure depending on the alignment of the orbitals between neighboring layers. Furthermore, it is demonstrated that these orbital-mediated effects provide a route to drive semiconductor-to-metal transitions with technologically pertinent gaps and on ultrafast timescales.
These results are particularly relevant for the ongoing development of novel, miniaturized and ultrafast devices based on layered transition metal dichalcogenides. The discovery of orbital textures also helps to explain a number of long-standing puzzles concerning the electronic self-organization in 1T-TaS2 : the ultrafast response to optical excitations, the high sensitivity to pressure as well as a mysterious commensurate phase that is commonly thought to be a special phase a so-called “Mott phase” and that is not found in any other isostructural modification.
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D'Acchioli, Jason S. "On the nature of the electronics structure of metal-metal quadruply bonded complexes". Connect to resource, 2005. http://rave.ohiolink.edu/etdc/view?acc%5Fnum=osu1126621699.
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Thesis (Ph. D.)--Ohio State University, 2005.Title from first page of PDF file. Document formatted into pages; contains xii, 286 p.; also includes graphics (some col.). Includes bibliographical references (p. 273-286). Available online via OhioLINK's ETD Center
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Venter, Gerhard (Gerhard Abraham). "An Ab Initio density functional study of the structure and stability of transition metal ozone complexes". Thesis, Stellenbosch : Stellenbosch University, 2002. http://hdl.handle.net/10019.1/52650.
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Thesis (MSc)--Stellenbosch University, 2002.ENGLISH ABSTRACT: A thorough search through the literature as well as through the Cambridge Crystallographic Structural Database resulted in no examples of a neutral ozone acting as ligand in a complex with any metal. Ionic compounds containing ozonide as anionic species, however, are well known throughout the literature and not surprisingly the only result for 0₃ and a metal in the CCSD was an ionic rubidium ozonide compound. What follows is a systematic study into the result of placing an ozone ligand within complexing distance of a transition metal (the first transition row from titanium to copper). Due to the novelty of the system, as first approximation four different orientations of the ozone ligand relative to the metal (a metal cation in these calculations) were investigated. It was found that coordination through the terminal oxygens resulted in energy minima for all the metal cations, although not necessarily the absolute energy minimum on the potential energy surface for the specific cation. A further structural study was done by adding carbonyl and hydrogen ligands to the system, according to the 18-electron rule. For these calculations coordination through the terminal oxygens was employed. In both series the dissociation energy was also calculated. The dissociation energies for the M(CO)nHm(0₃) complexes were all positive, indicating that they are theoretically stable structures. The resulting wave functions were then analysed with the help of three techniques: Atoms in Molecules (AIM), Charge Decomposition Analysis (CDA) and Natural Bond Orbital Analysis (NBO). AIM showed that bonds were indeed formed between the ozone ligand and the transition metal and hinted that the bonding model can be interpreted with the Dewar-Chatt-Duncanson (DCD) model of σ-donation and л-back donation. CDA confirmed that this was the case. NBO results proved erroneous due to the largely delocalized electronic structure of the complexes.
AFRIKAANSE OPSOMMING: 'n Deeglike soektog deur die literatuur en die Cambridge Crystallographic Structural Database het geen resultate gelewer van komplekse waarin 'n neutrale osoonligand komplekseer met 'n metaal nie. Ioniese verbindings waarin die osonied as anioon optree, is wel bekend deur die literatuur en die enigste resultaat in die CCSD - vir 'n soektog bevattende osoon en 'n metaal - het 'n rubidiumosonied-verbinding opgelewer. Wat volg is 'n stelselmatige studie om die effek te ondersoek indien 'n osoonligand naby genoeg aan 'n oorgangsmetaal geplaas word om kompleksering te bevoordeel (metale wat gebruik is, is die eerste oorgangsreeks vanaf titanium tot koper). As gevolg van die onbekendheid van die sisteem is vier verskillende oriëntasies van die osoonligand relatied tot die metal ('n metal katioon in die geval) as beginpunt ondersoek. Daar is gevind dat koordinasie deur die terminale suurstowwe van die osoonligand vir al die metal katione lei tot energie minima, alhoewel dié minima nie noodwendig die globale minima op die potensiële energie oppervlaktes van die katione is nie. 'n Verdere studie is gedoen deur karboniel- en waterstofligande tot die sisteem te voeg, gelei deur die 18-elektron reel. Vir hierdie berekeninge is koördinasie deur die terminale suurstowwe gebruik. In beide reeks is dissosiasie-energieë bereken. Die dissosiasie energieë van die M(CO)nHm(0₃) komplekse was deurgaan positief wat aandui dat die komplekse teoreties stabiel is. Die verkrygde golffunksies is hierna analiseer deur middel van drie tegnieke: Atoms in Molecules (AIM), Charge Decomposition Analysis (CDA) en Natural Bond Orbital Analysis (NBO). AIM het getoon dat bindings inderdaad gevorm word tussen die osoonligand en die metal en bet die moontlikheid laat ontstaan dat die bindingsmodel volgens die Dewar-Chatt-Duncason (DCD) model van σ-donasie en л-terugdonasie geïnterpreteer kan word. Hierdie waarneming is bevestig deur CDA. NBO resultate kon nie suksesvol gebruik word nie as gevolg van die hoë graad van electron delokalisasie van die komplekse.
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Kinzer, Raymond Edward. "Fourier transform infrared spectroscopy study of small transition-metal carbide clusters". [Fort Worth, Tex.] : Texas Christian University, 2009. http://etd.tcu.edu/etdfiles/available/etd-10152009-103514/unrestricted/kinzer.pdf.
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Tanaka, Yukio, Yasuhiro Asano y Alexander A. Golubov. "Shape of Cooper pairs in a normal-metal/superconductor junction". American Physical Society, 2008. http://hdl.handle.net/2237/11296.
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Wang, Siwen. "Orbital Level Understanding of Adsorbate-Surface Interactions in Metal Nanocatalysis". Diss., Virginia Tech, 2020. http://hdl.handle.net/10919/98923.
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We develop a theoretical framework for a priori estimation of catalytic activity of metal nanoparticles using geometry-based reactivity descriptors of surface atoms and kinetic analysis of reaction pathways at various types of active sites. We show that orbitalwise coordination numbers 𝐶𝑁α (α = 𝑠 or 𝑑) can be used to predict chemical reactivity of a metal site (e.g., adsorption energies of critical reaction intermediates) by being aware of the neighboring chemical environment, outperforming their regular (𝐶𝑁) and generalized (𝐶̅𝑁̅) counterparts with little added computational cost. Here we include two examples to illustrate this method: CO oxidation on Au (5𝑑¹⁰6𝑠¹) and O₂ reduction on Pt (5𝑑⁹6𝑠¹). We also employ Bayesian learning and the Newns-Anderson model to advance the fundamental understanding of adsorbate-surface interactions on metal nanocatalysts, paving the path toward adsorbate-specific tuning of catalysis.Doctor of Philosophy
The interactions between reaction intermediates and catalysts should be neither too strong nor too weak for catalytic optimization. This Sabatiers principle arising from the scaling relations among the energetics of reacting species at geometrically similar sites, provides the conceptual basis for designing improved catalysts, but imposes volcano-type limitations on the attainable catalytic activity and selectivity. One of the greatest challenges faced by the catalysis community today is how to develop design strategies and ultimately predictive models of catalytic systems that could circumvent energy scaling relations. This work brings the quantum-chemical modeling and machine learning technique together and develops a novel stochastic modeling approach to rationally design the catalysts with desired properties and bridges our knowledge gap between the empirical kinetics and atomistic mechanisms of catalytic reactions.
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Lin, Xi 1973. "First-principles density functional theory study of sulfur oxide chemistry on transition metal surfaces". Thesis, Massachusetts Institute of Technology, 2003. http://hdl.handle.net/1721.1/29642.
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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003.Vita.
Includes bibliographical references (p. 297-309).
In this thesis, the chemistry of sulfur oxides on transition metals is studied extensively via first-principles density functional theory (DFT) computations, focusing on the chemical reactivity and selectivity in sulfur poisoning chemical processes that address environmental concerns. The systematic approach we establish can be extended to general computational studies of small gas-phase molecules interacting with extended surfaces or finite-size clusters. The thesis starts with a theoretical presentation of modem quantum many-body theory that brings together mean-field theory, DFT, and Green's function quantum Monte Carlo theory. The essence of chemical reactivity theory in the framework of DFT is emphasized. The thesis continues with an extensive survey of the current status of sulfur oxide chemistry and an overall presentation of our computational approaches towards a detailed understanding of chemical reactivity and selectivity. The basic guidelines in chemical reactivity are systematically constructed by computed comprehensive thermodynamic data of surface S, O, SO, SO2, SO3, and S04 species as a function of coverage at low and intermediate temperatures. Under these basic guidelines, experimentally measured surface spectra are interpreted, contradictory experimental observations are resolved, and applicable experimental measurements are suggested for confirming computational predictions. Moreover, the chemical reactivity study is supplemented by our chemical kinetics study focusing on the catalytic oxidation of SO2 under oxygen rich conditions. This is the key process that hampers the implementation of the next-generation automotive catalytic converter. The revealed Langmuir-Hinshelwood mechanism demonstrates the essential catalytic performance of the Pt(1 11) surface.
(cont.) The thesis closes with a chemical selectivity analysis of the effects of catalyst particle size on chemisorption of gas-phase adatoms. In summary, the presentation of the chemistry of sulfur-containing molecules in this work is aimed at a scientific understanding of the strong poisoning effects in heterogeneous catalysis. However, the chemistry of sulfur-containing molecules has many more fundamental implications, such as in designing novel re-conjugated conducting devices for quantum computers. The underlying hybrid bonding flexibility of sulfur allows it to simultaneously bind to heavy transition metal atoms (such as Pt, Cu, or Au) and first-row atoms (such as oxygen atoms or carbon atoms in organic molecules).
by Xi Lin.
Ph.D.
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Martin, Claudia. "Density functional study of the electronic and magnetic properties of selected transition metal complexes". Doctoral thesis, Technische Universitaet Bergakademie Freiberg Universitaetsbibliothek "Georgius Agricola", 2014. http://nbn-resolving.de/urn:nbn:de:bsz:105-qucosa-134958.
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Die vorliegende Promotionsarbeit “Density functional study of the electronic and magnetic properties of selected transition metal complexes” beschäftigt sich mit dem Zusammenhang zwischen strukturellen Merkmalen sowie elektronischen und magnetischen Eigenschaften von Einzelmolekül-Magneten. Im Wesentlichen konnte dabei gezeigt werden, dass die magnetischen Eigenschaften sowohl von strukturellen Merkmalen als auch von den elektronischen Eigenschaften bestimmt werden. Des Weiteren ergab sich, dass verschiedene Kenngrößen der magnetischen Eigenschaften (im speziellen der magnetische Grundzustand S sowie die magnetische Anisotropie D) miteinander korreliert sind. Dies ist im Besonderen für eine mögliche Anwendung von Einzelmolekül-Magneten im Bereich der Datenspeicherung von Bedeutung.
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Melo, Leonardo de. "Powder jet particle density distribution analysis and qualification for the laser metal deposition process". reponame:Repositório Institucional da UFSC, 2015. https://repositorio.ufsc.br/xmlui/handle/123456789/171441.
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Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro Tecnológico, Programa de Pós-Graduação em Engenharia Mecânica, Florianópolis, 2015.Made available in DSpace on 2016-12-13T03:03:04Z (GMT). No. of bitstreams: 1 340514.pdf: 4063742 bytes, checksum: 6a2f911982008b177bc31b52c459c372 (MD5) Previous issue date: 2015
Abstract: The quality of the Laser Metal Deposition process depends on several factors and components. One of them and also one of the most important is the powder jet. Regular monitoring of the different variables involved on the powder jet need to be performed in order to assure the demanded high stability and quality standards of the produced coating layers. This monitoring is done through process monitoring techniques, where the powder jet is illuminated from the side, by a laser line, and recorded by a coaxially aligned camera through the powder feed nozzle. Symmetry, geometry and position of different levels of the powder jet can be analyzed through relevant algorithms. They also provide calculations of the particle density distribution the recorded images. The spatial particle density distribution of the powder jet can be calculated by superimposing individual levels along the jet. The measurement and monitoring principle was successfully tested with various nozzles and powder properties, making it possible to fully characterize a powder jet.
A qualidade do processo de deposição de metais a laser depende de diversos fatores e componentes. Um dos componentes mais importantes é o fluxo de pó metálico. É necessário o monitoramento contínuo das diferentes variáveis e parâmetros que influenciam no fluxo de pó para se garantir os altos padrões de qualidade e estabilidade requeridos nas peças produzidas. Este monitoramento é realizado através de técnicas de controle de processos, onde o fluxo de pó metálico é iluminado lateralmente, por um laser de iluminação em formato de linha, e gravado por uma câmera coaxial ao bocal alimentador de pó. Simetria, geometria e posição de diferentes níveis do fluxo de pó podem ser analisados através de algoritmos relevantes. Tais algoritmos tornam possíveis também cálculos da distribuição das partículas no fluxo, através da sobreposição de imagens de todos os frames gravados no vídeo em cada nível do fluxo de pó. O processo de medição e análise foi testado com sucesso em diferentes bocais alimentadores de pó e com diferentes materiais e parâmetros do fluxo, tornando possível sua caracterização e qualificação.
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Liu, Haitao. "Novel 3-D CMOS and BiCMOS devices for high-density and high-speed ICs /". View Abstract or Full-Text, 2003. http://library.ust.hk/cgi/db/thesis.pl?ELEC%202003%20LIU.
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Weerawardene, K. L. Dimuthu M. "Optical and luminescence properties of noble metal nanoparticles". Diss., Kansas State University, 2017. http://hdl.handle.net/2097/38189.
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Doctor of PhilosophyDepartment of Chemistry
Christine M. Aikens
The remarkable optical and luminescence properties of noble metal nanoparticles (with diameters < 2 nm) attract researchers due to potential applications in biomedicine, photocatalysis, and optoelectronics. Extensive experimental investigations on luminescence properties of thiolate-protected gold and silver nanoclusters during the past decade have failed to unravel their exact photoluminescence mechanism. Herein, density functional and time-dependent density functional theory (DFT and TDDFT) calculations are performed to elucidate electronic-level details of several such systems upon photoexcitation. Multiple excited states are found to be involved in photoemission from Au₂₅(SR)₁₈– nanoclusters, and their energies agree well with experimental emission energies. The Au₁₃ core-based excitations arising due to electrons excited from superatom P orbitals into the lowest two superatom D orbitals are responsible for all of these states. The large Stokes shift is attributed to significant geometrical and electronic structure changes in the excited state. The origin of photoluminescence of Ag₂₅(SR)₁₈– nanoclusters is analogous to their gold counterparts and heteroatom doping of each cluster with silver and gold correspondingly does not affect their luminescence mechanism. Other systems have been examined in this work to determine how widespread these observations are. We observe a very small Stokes shift for Au₃₈(SH)₂₄ that correlates with a relatively rigid structure with small bond length changes in its Au₂₃ core and a large Stokes shift for Au₂₂(SH)₁₈ with a large degree of structural flexibility in its Au₇ core. This suggests a relationship between the Stokes shift of gold−thiolate nanoparticles and their structural flexibility upon photoexcitation. The effect of ligands on the geometric structure and optical properties of the Au₂₀(SR)₁₆ nanocluster is explored. Comparison of the relative stability and optical absorption spectra suggests that this system prefers the [Au₇(Au₈SR₈)(Au₃SR₄)(AuSR₂)₂] structure regardless of whether aliphatic or aromatic ligands are employed. The real-time (RT) TDDFT method is rapidly gaining prominence as an alternative approach to capture optical properties of molecular systems. A systematic benchmark study is performed to demonstrate the consistency of linear-response (LR) and RT-TDDFT methods for calculating the optical absorption spectra of a variety of bare gold and silver nanoparticles with different sizes and shapes.
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Huang, Chender 1960. "Characterization of interface trap density in power MOSFETs using noise measurements". Thesis, The University of Arizona, 1988. http://hdl.handle.net/10150/276872.
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Low-frequency noise has been measured on commercial power MOSFETs. These devices, fabricated with the VDMOS structure, exhibit a 1/f type noise spectrum. The interface state density obtained from noise measurements was compared with that obtained from the subthreshold-slope method. Reasonable agreement was found between the two measurements. The radiation effects on the noise power spectral density were also investigated. The results indicated that the noise can be attributed to the generation of interface traps near the Si-SiO₂ interface. The level of interface traps generated by radiation was bias dependent. The positive gate bias gave rise to the largest interface-trap density.
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Vaddadi, Sridhar. "Computational Studies of Coordinatively Unsaturated Transition Metal Complexes". Thesis, University of North Texas, 2006. https://digital.library.unt.edu/ark:/67531/metadc5488/.
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In this research the validity of various computational techniques has been determined and applied the appropriate techniques to investigate and propose a good catalytic system for C-H bond activation and functionalization. Methane being least reactive and major component of natural gas, its activation and conversion to functionalized products is of great scientific and economic interest in pure and applied chemistry. Thus C-H activation followed by C-C/C-X functionalization became crux of the synthesis. DFT (density functional theory) methods are well suited to determine the thermodynamic as well as kinetic factors of a reaction. The obtained results are helpful to industrial catalysis and experimental chemistry with additional information: since C-X (X = halogens) bond cleavage is important in many metal catalyzed organic syntheses, the results obtained in this research helps in determining the selectivity (kinetic or thermodynamic) advantage. When C-P bond activation is considered, results from chapter 3 indicated that C-X activation barrier is lower than C-H activation barrier. The results obtained from DFT calculations not only gave a good support to the experimental results and verified the experimentally demonstrated Ni-atom transfer mechanism from Ni=E (E = CH2, NH, PH) activating complex to ethylene to form three-membered ring products but also validated the application of late transition metal complexes in respective process. Results obtained supported the argument that increase in metal coordination and electronic spin state increases catalytic activity of FeIII-imido complexes. These results not only encouraged the fact that DFT and multi-layer ONIOM methods are good to determine geometry and thermodynamics of meta-stable chemical complexes, but also gave a great support to spectroscopic calculations like NMR and Mossbauer calculations.
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Cranswick, Matthew A. "Gas-phase Photoelectron Spectroscopy and Computational Studies of Metal-thiolate Interactions: Implications to Biological Electron Transfer". Diss., The University of Arizona, 2008. http://hdl.handle.net/10150/195569.
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The research outlined in this dissertation focuses on understanding the role of metal-sulfur interactions as applied to bioinorganic and organometallic systems. This metal-sulfur interaction is analyzed using both gas-phase photoelectron spectroscopy (PES) and density functional theory (DFT). Gas-phase photoelectron spectroscopy is the most direct probe of electronic structure and is used in these studies to probe the molecular orbital energy levels of these model compounds, giving rise to an understanding of the metal and sulfur orbital interactions and characters (i.e. is an orbital primarily metal or sulfur based). Using density functional theory, orbital energies, overlap, and characters can be calculated and complement the PES experiments allowing for a detailed understanding of the electronic structure. The first part of my dissertation explains the design and implementation of a dual source gas-phase ultraviolet/X-ray photoelectron spectrometer (UPS/XPS). This gas-phase UPS/XPS can be used to quantify the bonding/antibonding character of frontier molecular orbitals, with specific applications to metal-sulfur interactions, allowing for a thorough analysis of the metal-sulfur interaction. The second part of the dissertation explores using model complexes, of the type Cp₂V(dithiolate) (where Cp is cyclopentadienyl and dithiolate is 1,2-ethenedithiolate or 1,2-benzenedithiolate), along with PES and DFT calculations to investigate the role of the pyranopterindithiolate cofactor and the d¹ electron configuration in modulating the redox potential and electron transfer in the active sites of molybdenum enzymes. This study shows that the d¹ electronic configuration offers a low energy electron transfer pathway for the reoxidation of the active site molybdenum center. The third part of the dissertation explores the use of model compounds that specifically focus on iron-thiolate interactions in biological systems, and the effect of electronic energy matching and sterics on the oxidation potential of this interaction. This study has shown that the metal-sulfur interaction is sensitive to the orientation of the thiolate ligand, and that during oxidation an “electronic-buffering effect” makes assigning a formal oxidation state to the metal center almost meaningless. All of these studies illustrate how the thiolate ligand can modulate the electron density and oxidation potential of the metal-sulfur interaction and the implication of this interaction to biological electron transfer.
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Li, Qiang. "Density functional theory studies of biomass conversion on metal surfaces: from small to large molecules". Doctoral thesis, Universitat Rovira i Virgili, 2017. http://hdl.handle.net/10803/461081.
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En aquesta tesi s'han proposat i calculat una sèrie de mecanismes de reacció relacionats amb diverses molècules derivades de biomassa sobre models de superficie utilitzant el paquet VASP (Vienna Ab initio simulation package).
S'ha realitzat una investigació multiescala sobre formació d'hidrogen a partir de petites molècules de metanol, etanol, etilenglicol i glicerol. Els càlculs dels alcohols C1 i C2 es realitzaren en superfícies de Cu(111) i Ru(0001), mentre que els de glicerol només sobre Ru(0001). Es van optimitzar les geometries d'enllaç dels intermedis complets, així com s'ha proposat la descomposició detallada i els mecanismes d'hidrogenació relacionats amb dites espècies. S'han analitzat les relacions BEP i TSS i s'ha realitzat també una simulació microcinètica ab initio sota diferents condicions.
Hidrogenació d'àcid levulínic a gamma-valerolactona sobre Ru(0001) i sobre Ru(0001) decorada amb HHDMA. S'ha proposat el mecanisme de formació de l'anell intramolecular sobre la superfície de Ru(0001). S'ha elucidat l'acidesa interfacial i les estructures locals a la interfície HHDMA-Ru(0001) que promouen la velocitat de catàlisi i l'estabilitat front l'oxidació.
Hidrogenació de glucosa i manosa als seus alcohols de sucre a la superfície Ru(0001). Les reaccions dels isòmers lineals i cíclics han estat calculades i comparades entre dues molècules de sucre i amb els resultats experimentals. L'autor va trobar que concentracions de diferents isòmers reactius en la fase líquida, diferents energies d'adsorció i mecanismes de reacció treballen conjuntament per controlar les velocitats de reacció totals.
Descomposició i hidrogenació de lignina a les superfícies Ni(111) i Ni(111)dopades amb Ru. S'han aclarit els mecanismes de descomposició de lignina basats en un model de dimer més complicat. S'han discutit els efectes de l'estereocentre en les seves conversions i també s’han dilucidat els efectes de dopatge de Ru promocionant el comportament dels catalitzadors.En esta tesis se han propuesto y calculado una serie de mecanismos de reacción relacionados con diversas moléculas derivadas de biomasa sobre modelos de superficie usando el paquete VASP (Vienna Ab initio simulation package). Se ha realizado una investigación multiescala sobre formación de hidrógeno a partir de moléculas pequeñas de metanol, etanol, etilenglicol y glicerol. Los cálculos de los alcoholes C1 y C2 se realizaron en superficies de Cu(111) y Ru(0001), mientras que los de glicerol sólo en Ru(0001). Se optimizaron las geometrías de enlace de los intermedios completos, así como se ha propuesto la descomposición detallada y los mecanismos de hidrogenación relacionados con dichas especies. Se han analizado las relaciones BEP y TSS y se ha realizado también una simulación microcinética ab initio en diferentes condiciones. Hidrogenación de ácido levulínico a gamma-valerolactona sobre Ru(0001) y sobre Ru(0001) decorada con HHDMA. Se ha propuesto el mecanismo de formación del anillo intramolecular en la superficie de Ru(0001). Se ha elucidado la acidez interfacial y las estructuras locales en la interfaz HHDMA-Ru(0001) que promueven la velocidad de catálisis y la estabilidad frente a la oxidación. Hidrogenación de glucosa y manosa a sus alcoholes de azúcar sobre la superficie de Ru(0001). Las reacciones de los isómeros lineales y cíclicos se han calculado y comparado entre dos moléculas de azúcar y con los resultados experimentales. El autor encontró que concentraciones de diferentes isómeros reactivos en la fase líquida, diferentes energías de adsorción y mecanismos de reacción trabajan juntos para controlar las velocidades de reacción totales. Descomposición de lignina e hidrogenación sobre superficies de Ni(111) y Ni(111) dopadas con Ru. Se han esclarecido los mecanismos de descomposición de la lignina basados en un modelo de dímero más complicado. Los efectos del estereocentro en sus conversiones se han discutido y los efectos de dopaje de Ru promocionando el comportamiento de los catalizadores también se ha aclarado.
In this thesis, a series of surface reaction mechanisms related with various biomass derived molecules on slab models have been proposed and computed by using the Vienna Ab initio simulation package (VASP). 1 Multiscale investigation of hydrogen releasing from small molecules of methanol, ethanol, ethylene glycol, and glycerol have been studied. C1 and C2 alcohols’ calculations are performed both on Cu(111) and Ru(0001) surfaces and glycerol is on Ru(0001). Complete intermediates binding geometries were optimized, detailed decomposition, hydrogenation mechanisms related with these species have been proposed. BEP and TSS relationship have been analyzed and ab initio microkinetic simulation under different conditions has been also performed. 2 Glucose and mannose hydrogenation to their sugar alcohols on Ru(0001) surface. Reactions from linear and ring isomers have been calculated and compared between two sugar molecules, and compared with experiment results. The author found that concentrations of different reactant isomers in the liquid phase, different adsorption energies and reaction mechanisms work together to control the overall reaction rates. 3 Levulinic acid hydrogenation to gamma-valerolactone on Ru(0001) and HHDMA decorated Ru(0001) surface. Intramolecular ring formation mechanism on Ru(0001) surface has been outlined. Interfacial acidity and local structures in the HHDMA-Ru(0001) interface which promote the catalysis rate and stability against oxidation have been illuminated. 4 Lignin decomposition and hydrogenation on Ni(111) and Ru doped Ni(111) surfaces. Lignin decomposition mechanisms based on more complicated dimer model have been clarified. Stereocenter effects in its conversions have been discussed and the Ru doping effects on promoting the catalysts behavior is also elucidated.
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Sheen, Paul David. "Towards a hybrid density functional theory and molecular mechanics model for large transition metal systems". Thesis, University of Bath, 1995. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.296297.
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Kulkarni, B. S. "Structure and reactivity study of beta zeolite and al metal clusters using density functional theory". Thesis(Ph.D.), CSIR-National Chemical Laboratory, Pune, 2010. http://dspace.ncl.res.in:8080/xmlui/handle/20.500.12252/3753.
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