Current Search: Kaden, William (x)
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- Title
- A Theoretical Investigation of Small Organic Molecules on Transition Metal Surfaces.
- Creator
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Malone, Walter, Kara, Abdelkader, Stolbov, Sergey, Kaden, William, Thomas, Jayan, University of Central Florida
- Abstract / Description
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With the ever growing number of proposed desnity functional theory (DFT) functionals it becomes necessary to thoroughly screen any new method to determine its merit. Especially relevant methods include a proper description of the van der Waals (vdW) interaction, which can prove vital to a correct description of a myriad of systems of technological importance. The first part of this dissertation explores the utility of several vdW-inclusive DFT functionals including optB86b-vdW, optB88-vdW,...
Show moreWith the ever growing number of proposed desnity functional theory (DFT) functionals it becomes necessary to thoroughly screen any new method to determine its merit. Especially relevant methods include a proper description of the van der Waals (vdW) interaction, which can prove vital to a correct description of a myriad of systems of technological importance. The first part of this dissertation explores the utility of several vdW-inclusive DFT functionals including optB86b-vdW, optB88-vdW, optPBE-vdW, revPBE-vdW, rPW86-vdW2, and SCAN+rVV10 by applying them to model systems of small organic molecules, pyridine and thiophene, on transition metal surfaces. Overall, we find the optB88-vdW functional gives the best, most balanced description of both thiophene and pyridine on transition metal surfaces while revPBE-vdW, rPW86-vdW2, and SCAN+rVV10 functionals perform especially poorly for these systems. In the second part of this dissertation we change our focus to potential applications of DFT. Specifically, we study the hydrodesulfurization (HDS) process and molecules that could be used in molecular electronics. The removal of sulfur containing molecules from petrochemicals through HDS is an exceptionally important process economically, and the field of molecular electronics is rapidly developing with hopes of competing with and replacing their silicon analogues. First we investigate the hydrodesulfurization of thiophene. In this dissertation we manage to map the HDS rate of thiophene in realistic reaction conditions to the charge transfer and adsorption energy of thiophene on bare transition metal surfaces in hopes of predicting ever more active HDS catalysis. Finally we look at the adsorption of polythiophenes and 5,14-dihydro-5,7,12,14-tetraazapentacene (DHTAP) on Au(111) and Cu(110). We find that polythiophenes may dissociate of Au(111), presenting an issue for their use in molecular electronics. DHTAP, in contrast, proves to a suitable candidate for use practical devices.
Show less - Date Issued
- 2019
- Identifier
- CFE0007494, ucf:52653
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007494
- Title
- Growth and doping of MoS2 thin films for electronic and optoelectronic applications.
- Creator
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Abouelkhair, Hussain, Peale, Robert, Kaden, William, Stolbov, Sergey, Coffey, Kevin, University of Central Florida
- Abstract / Description
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MoS2 high absorption coefficient, high mobility, mechanical flexibility, and chemical inertness is very promising for many electronic and optoelectronic applications. The growth of high-quality MoS2 by a scalable and doping compatible method is still lacking. Therefore, the suitable dopants for MoS2 are not fully explored yet. This dissertation consists mainly of four main studies. The first study is on the growth of MoS2 thin films by atmospheric pressure chemical vapor deposition. Scanning...
Show moreMoS2 high absorption coefficient, high mobility, mechanical flexibility, and chemical inertness is very promising for many electronic and optoelectronic applications. The growth of high-quality MoS2 by a scalable and doping compatible method is still lacking. Therefore, the suitable dopants for MoS2 are not fully explored yet. This dissertation consists mainly of four main studies. The first study is on the growth of MoS2 thin films by atmospheric pressure chemical vapor deposition. Scanning electron microscope images revealed the growth of microdomes of MoS2 on top of a smooth MoS2 film. These microdomes are very promising as a broadband omnidirectional light trap for light harvesting applications. The second study is on the growth of MoS2 thin films by low pressure chemical vapor deposition (LPCVD). Control of sulfur vapor flow is essential for the growth of a pure phase of MoS2. Turning off sulfur vapor flow during the cooling cycle at 700 (&)#186;C leads to the growth of highly textured MoS2 with a Hall mobility of 20 cm2/Vs. The third study was on the growth of Ti-doped MoS2 thin films by LPCVD. The successful doping was confirmed by Hall effect measurement and secondary ion mass spectrometry (SIMS). Different growth temperatures from 1000 to 700 ? were studied. Ti act as a donor in MoS2. The fourth study is on fluorine-doped SnO2 (FTO) which has many technological applications including solar cells and transistors. FTO was grown by an aqueous-spray-based method. The main objective was to compare the actual against the nominal concentration of fluorine using SIMS. The concentration of fluorine in the grown films is lower than the concentration of fluorine in the aqueous solution.?
Show less - Date Issued
- 2017
- Identifier
- CFE0006847, ucf:51767
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006847
- Title
- Tuning chemical and optical properties of nanomaterials: From extended surfaces to finite nanoclusters.
- Creator
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Hooshmand Gharehbagh, Zahra, Rahman, Talat, Kara, Abdelkader, Kaden, William, Uribe Romo, Fernando, University of Central Florida
- Abstract / Description
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Modifying the electronic and optical properties of surfaces and nanostructures are in the forefront of surface science. This dissertation's focus is on this problem. The first part is on the adsorption of functionalized naphthalene molecules on Cu(111) surface. The results show that changing the functional group results in modification of charge redistribution at the interface of molecule and surface and the electronic structure of Cu changes. The second part discusses the new Moir(&)#233;...
Show moreModifying the electronic and optical properties of surfaces and nanostructures are in the forefront of surface science. This dissertation's focus is on this problem. The first part is on the adsorption of functionalized naphthalene molecules on Cu(111) surface. The results show that changing the functional group results in modification of charge redistribution at the interface of molecule and surface and the electronic structure of Cu changes. The second part discusses the new Moir(&)#233; structure of h-BN on Rh(111) induced by intrinsic carbon impurities of Rh single crystals. We found that these impurities intercalate between h-BN and Rh(111) with new local properties such as charge transfer from Rh and C atoms to h-BN such as appearance of new states in the BN. The third part is about the study of CO super lattice structure at 1/2ML when adsorbed on Pd(111). By considering all the possible overlayer structures and using several different functionals, we found that two structures can be made by CO adsorbents and all the other structures convert to one of these two. The fourth part is on the electronic and optical properties of ligated Ag44 nanoclusters. Using DFT and TDDFT calculations we show that when the pH level of a solvent is changed, the protecting ligands deprotonate and their interaction with each other as well as the metal core varies and the new peaks in absorption spectrum arise from electron rich deprotonated ligands. The final part is on the adsorption of planar molecules on MoS2. We found that the isomers of di-iodobenzene adsorb with same strength on MoS2 and it is the symmetry of frontier orbitals that identifies their different behavior. Also the adsorption and dissociation of benzenethiol on MoS2 was studied and the results show that benzenethiol dissociates only in the presence of defects and heals the structure.
Show less - Date Issued
- 2018
- Identifier
- CFE0007337, ucf:52138
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007337
- Title
- Experimental confirmation of ballistic nanofriction and quasiparticle interference in Dirac materials.
- Creator
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Lodge, Michael, Ishigami, Masahiro, Kaden, William, Schelling, Patrick, Del Barco, Enrique, Roy, Tania, University of Central Florida
- Abstract / Description
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This dissertation is broadly divided into two parts. The first part details the development and usage of an experimental apparatus to measure the dry nanofriction for a well-defined interface at high sliding speeds. I leverage the sensitivity of a quartz crystal microbalance (QCM) to determine the drag coefficient of an ensemble of gold nanocrystals sliding on graphene at speeds up to 11 cm/s. I discuss the theories of velocity-dependent friction, especially at high sliding speeds, and QCM...
Show moreThis dissertation is broadly divided into two parts. The first part details the development and usage of an experimental apparatus to measure the dry nanofriction for a well-defined interface at high sliding speeds. I leverage the sensitivity of a quartz crystal microbalance (QCM) to determine the drag coefficient of an ensemble of gold nanocrystals sliding on graphene at speeds up to 11 cm/s. I discuss the theories of velocity-dependent friction, especially at high sliding speeds, and QCM modeling. I also discuss our synthesis protocols for graphene and molybdenum disulfide, as well as our protocol for fabricating a clean, graphene-laminated QCM device and nanocrystal ensemble. The design and fabrication of our QCM oscillator circuit is presented in detail. The quantitatively-measured the drag coefficient is compared against molecular dynamics simulations at both low and high sliding speeds. We show evidence of a predicted ultra-low friction regime and find that the interaction energy between gold nanocrystals and graphene is lower than previously assumed. In the second part of this dissertation, I detail the band structure measurement of a novel semimetal using scanning tunneling microscopy. In particular, I measured the energy-dependenceof quasiparticle interference patterns at the surface of zirconium silicon sulfide (ZrSiS), a topological nodal line semimetal whose charge carrier quasiparticles possess a pseudospin degree offreedom. The aims of this study were to (1) discover the shape of the band structure above the Fermi level along a high-symmetry direction, (2) discover the energetic location of the line node inthe same high-symmetry direction, and (3) discover the selection rules for k transitions. This study confirms the predicted linearity in E(k) of the band structure above the Fermi level. Additionally,we observe an energy-dependent mechanism for pseudospin scattering. This study also provides the first experimentally-derived estimation of the line node position in E(k).
Show less - Date Issued
- 2018
- Identifier
- CFE0007218, ucf:52222
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007218
- Title
- Quantum Chemical Studies for the Engineering of Metal Organic Materials.
- Creator
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Rivera Jacquez, Hector, Masunov, Artem, Balaeff, Alexander, Harper, James, Heider, Emily, Zou, Shengli, Kaden, William, University of Central Florida
- Abstract / Description
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Metal Organic Materials (MOM) are composed of transition metal ions as connectors and organic ligands as linkers. MOMs have been found to have high porosity, catalytic, and optical properties. Here we study the gas adsorption, color change, and non-linear optical properties of MOMs. These properties can be predicted using theoretical methods, and the results may provide experimentalists with guidance for rational design and engineering of novel MOMs. The theory levels used include semi...
Show moreMetal Organic Materials (MOM) are composed of transition metal ions as connectors and organic ligands as linkers. MOMs have been found to have high porosity, catalytic, and optical properties. Here we study the gas adsorption, color change, and non-linear optical properties of MOMs. These properties can be predicted using theoretical methods, and the results may provide experimentalists with guidance for rational design and engineering of novel MOMs. The theory levels used include semi-empirical quantum mechanical calculations with the PM7 Hamiltonian and, Density Functional Theory (DFT) to predict the geometry and electronic structure of the ground state, and Time Dependent DFT (TD-DFT) to predict the excited states and the optical properties.The molecular absorption capacity of aldoxime coordinated Zn(II) based MOMs (previously measured experimentally) is predicted by using PM7 Theory level. The 3D structures were optimized with and without host molecules inside the pores. The absorption capacity of these crystals was predicted to be 8H2 or 3N2 per unit cell. When going beyond this limit, the structural integrity of the bulk material becomes fractured and microcrystals are observed both experimentally and theoretically.The linear absorption properties of Co(II) based complexes are known to change color when the coordination number is altered. In order to understand the mechanism of this color change TD-DFT methods are employed. The chromic behavior of the Co(II) based complexes studied was confirmed to be due to a chain in coordination number that resulted in lower metal to ligand distances. These distances destabilize the occupied metal d orbitals, and as a consequence of this, the metal to ligand transition energy is lowered enough to allow the crystals to absorb light at longer wavelengths.Covalent organic frameworks (COFs) present an extension of MOM principles to the main group elements. The synthesis of ordered COFs is possible by using predesigned structures andcarefully selecting the building blocks and their conditions for assembly. The crystals formed by these systems often possess non-linear optical (NLO) properties. Second Harmonic Generation (SHG) is one of the most used optical processes. Currently, there is a great demand for materials with NLO optical properties to be used for optoelectronic, imaging, sensing, among other applications. DFT calculations can predict the second order hyperpolarizability ?2 and tensor components necessary to estimate NLO. These calculations for the ?2 were done with the use of the Berry's finite field approach. An efficient material with high ?2 was designed and the resulting material was predicted to be nearly fivefold higher than the urea standard.Two-photon absorption (2PA) is another NLO effect. Unlike SHG, it is not limited to acentric material and can be used development of in vivo bio-imaging agents for the brain. Pt(II) complexes with porphyrin derivatives are theoretically studied for that purpose. The mechanism of 2PA enhancement was identified. For the most efficient porphyrin, the large 2PA cross-section was found to be caused by a HOMO-LUMO+2 transition. This transition is strongly coupled to 1PA allowed Q-band HOMO-LUMO states by large transition dipoles. Alkyl carboxyl substituents delocalize the LUMO+2 orbital due to their strong ?-acceptor effect, enhancing transition dipoles and lowering the 2PA transition to the desirable wavelengths range.The mechanism 2PA cross-section enhancement of aminoxime and aldoxime ligands upon metal addition of is studied with TD-DFT methods. This mechanism of enhancement is found to be caused by the polarization of the ligand orbitals by the metal cation. After polarization an increase in ligand to ligand transition dipole moment. This enhancement of dipole moment is related to the increase in 2PA cross-sections.
Show less - Date Issued
- 2015
- Identifier
- CFE0005990, ucf:50777
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005990