Diamond-like semiconductors (DLSs) are a class of semiconductor materials having structures similar to that of either cubic or hexagonal diamond. These normal valence compounds are of interest for their wide variety of technologically useful properties that can be tuned for specific applications. Until recently, DLS research has been focused on binary and ternary compositions due to their relative ease of synthesis. However, quaternary DLSs have gained considerable popularity due to their increased compositional flexibility and their potential as multifunctional materials. Despite their growing reputation, the vast number of possible combinations and conceivable solid solutions, DLSs remain fairly unexplored.<br>This work focuses on quaternary DLSs of the formula Ag2-II-IV-S4 in order to advance the knowledge of structure-property relationships for this entire class of materials. Toward this goal, a more complete understanding of the crystal structures of these materials is necessary. This task is often problematic due to the presence of isoelectronic, or nearly isoelectonic elements, that can complicate X-ray structure refinements. In this work, Ag2CdGeS4 is used as a case study to demonstrate that this problem can be resolved with careful consideration of bonding environments as well as the use of high-resolution X-ray sources. For the novel DLS Ag2ZnSiS4, the relationship between the structure and optical properties is probed with the combination of single crystal X-ray diffraction, optical diffuse reflectance spectroscopy and electronic structure calculations using the software package Wien2k. Finally, the current set of predictive tools employed to forcast diamond-like structures are reviewed, including the adherence of these guidelines to the novel compound Ag2FeSiS4 as well all over 60 ternary and quaternary diamond-like materials currently reported in the literature. Furthermore, the most common radii sets used for the prediction of bond distance and cell parameters in these materials are compared to the observed bond distances in quaternary diamond-like nonoxide materials. / Bayer School of Natural and Environmental Sciences / Chemistry and Biochemistry / PhD; / Dissertation;

Thermoelectric energy (TE) conversion can be used to create electricity from temperature gradients. Hence power can be generated from waste heat using TE materials, e.g. from the exhaust in automotives. This power in turn may lead to a reduction of gas consumption by reducing the alternator load on the engine. Because of the increasing demand and limited availability of energy sources, there is strong and renewed interest in advancing thermoelectric materials. Past research shows that the best TE materials are narrow band gap semiconductors composed of heavy elements, exhibiting a large Seebeck coefficient, S, combined with high electrical conductivity, σ, and low thermal conductivity, κ. Various research projects have been attempted during the past four years of my Ph.D. studies. These include the synthesis, crystal structure studies, electronic structure calculations and thermoelectric properties of transition metal oxides and thallium main group chalcogenides. Because of the good thermal stability, lack of sensitivity to the air, and non-toxicity, transition metal oxides are potential candidates for commercial thermoelectric applications. During the investigation of oxides for thermoelectric application, several interesting features of different transition metal oxides have been discovered: 1. A new quaternary layered transition-metal oxide, Na2Cu2TeO6, has been synthesized under air using stoichiometric mixtures of Na2CO3, CuO and TeO2. Na2Cu2TeO6 crystallizes in a new structure type, monoclinic space group C2/m with a = 5.7059(6) Å, b = 8.6751(9) Å, c = 5.9380(6) Å,  = 113.740(2)°, V = 269.05(5) Å3 and Z = 2, as determined by single crystal X-ray diffraction. The structure is composed of[Cu2TeO6] layers with the Na atoms located in the octahedral voids between the layers. Na2Cu2TeO6 is a green nonmetallic compound, in agreement with the electronic structure calculation and electrical resistance measurement. 2. An n-type narrow band gap semiconductor, LaMo8O14, exhibiting the high Seebeck coefficient of -94 μVK-1 at room temperature has been investigated. 3. Pb0.69Mo4O6 with a new modulated structure and stoichiometry was determined from single-crystal X-ray diffraction data. The compound crystallizes in the tetragonal super space group, P4/mbm(00g)00ss, with a = 9.6112(3) Å, c = 2.8411(1) Å, q = 0.25c*, which is different from the previously reported structure. As for the research of thermoelectric properties of thallium main group chalcogenides, three new ternary thallium selenides, Tl2.35Sb8.65Se14, Tl1.97Sb8.03Se13 and Tl2.04Bi7.96Se13, have been discovered. All three compounds crystallize in the same space group P21/m with different cell parameters, and in part different Wyckoff sites, hence different structure types. The three selenides with similar structures are composed of distorted edge-sharing (Sb,Bi)Se6 octahedra, while the distorted Tl/(Sb, Bi) sites are coordinated by 8 - 9 Se atoms. Electronic structure calculations and physical property measurements reveal they are semiconductors with high Seebeck coefficient but low electrical conductivity, and therefore not good thermoelectrics. On the other hand, our transport property measurements on the unoptimized Tl2SnTe3 sample show interesting thermoelectric properties of this known compound. Advanced thermoelectrics are dominated by antimonides and tellurides so far. The structures of the tellurides are mostly composed of NaCl-related motifs, hence do not contain any Te–Te bonds. All of the antimonide structures containing Sb–Sb bonds of various lengths are much more complex. The Sb atom substructures are Sb24– pairs in β-Zn4Sb3, linear Sb37– units in Yb14MnSb11, planar Sb44– rectangles in the skutterudites, e.g., LaFe3CoSb12, and Sb8 cubes interconnected via short Sb–Sb bonds to a three-dimensional network in Mo3Sb5Te2. The results of electronic structure calculations suggested that these interactions have a significant impact on the band gap size as well as on the effective mass around the Fermi level, which represent vital criteria for advanced thermoelectrics. The crystal structure and electronic structure investigation for the unique T net planar Sb–Sb interactions in Hf5Sb9 will be also presented, although Hf5Sb9 is metallic compound with poor thermoelectric performances.

Abstract The search for nanoscale active electronic devices has been an important objective in nanoscience and nanotechnology. In this study, the electronic and transport properties of the benzene-1,4-dithiol-molecule (BDT) and Au-atom-S-benzene-ring-O-(SBO)-Au-atom junctions and the Au-AlN(0001)-Au polar semiconductor junction have been calculated using the first-principles calculation method and a new integrated piecewise thermal equilibrium approach for the current. The current-voltage (I-V) and conductance-voltage (C-V) characteristic curves obtained for the Au-BDT-Au molecular junction agreed reasonably well with experimental ones. The study of Au-BDT-Au identifies that treating Au 5d electrons as core electrons and letting the S end of BDT be bonded to the Au surface directly overestimated the current. Calculated I-V characteristic curve revealed that the asymmetric Au-SBO-Au molecular junction has a pulse-like I-V characteristic curve with dual differential conductance, which resembled well the one observed experimentally. The analysis of the electronic structures showed that this dual differential conductance transport property was due to a subtle charge transfer at the electrode-molecule contacts. The calculated J-V characteristic curve of the Au-Al(0001)-Au junction shows coexistence of ohmic, switching effect and negative differential conductance. The electronic structure calculations show the existence of an intrinsic band tilt due to the polar nature of the AlN(0001) film, which gives rise to an asymmetric transport property of the junction and the presence of hole states at the N-surface side and interface states at the Al-surface side of the AlN film. The bias induced changes of the hole states, interface states and the states of the Al and N ions in central layers in the vicinity of the local chemical potential give rise to the interesting transport property of the Au-AlN(0001)-Au junction.

Intermolecular potential energy functions for CO2 have been developed from first principles for use in heterogeneous systems, including one with explicit polarization. The intermolecular potentials have been expressed in a transferable form and parameterized from nearly exact electronic structure calculations. Models with and without explicit many-body polarization effects, known to be important in simulation of interfacial processes, are constructed. The models have been validated on pressure-density isotherms of bulk CO2 and adsorption in three metal-organic framework (MOF) materials. The present models appear to offer advantages over high quality fluid/liquid state potentials in describing CO2 interactions in interfacial environments where sorbates adopt orientations not commonly explored in bulk fluids. Thus, the nonpolar CO2-PHAST and polarizable CO2-PHAST* potentials are recommended for materials/interfacial simulations.

In this dissertation, the applications of many-body physics in neutral bosons and electronic systems in transition metal oxides are discussed. In the first part of the thesis, I will introduce the concepts of Bose condensation, emphasize the significance of the order parameter in superfluids (macroscopic wave function), and its consequence such as the emergence of exotic vortex states under rotation. Dated back to the importance of the vortex dynamics in the properties of high T[subscript c] superconductors, people have introduced a dual vortex description to describe the dynamics of charged bosons in a magnetic field. Similarly, the dual description is adapted to the problems of neutral bosons under rotation. Based on that picture, vortices behave like charges in an effective magnetic field which has been known to demonstrate different quantum phases such as Wigner crystal phase, and fractional quantum Hall liquid phases depending on the relative fraction of the number of bosons and vortices. In this work, we would like to address the validity of the picture by low energy effective theory. We can identify the origin of the vortex masse and the parameter regimes in which the vortex dual description is appropriate. In the second part of the dissertation, density functional theory is used to describe the strongly correlated matters with local density approximation and local Hubbard U interaction(LDA+U). We are particularly interested in the interface states in the heterojunction systems of two different perovskite oxides. What we found is that the interface states can be engineered to appear in certain transitional metal oxide layers by controlling the number of positive and negative charged layers, leading to the formation of quantum wells in two dimension. This type of systems ignite the hope to search for broken symmetry states in the interface which can be tunable with chemical doping or electric field doping. Even room temperature superconducting state may or may not exist in the interface is still an intriguing issue. / text

Hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) is one of the most abundant materials in mammal bone. It crystallizes in an aqueous environment within spaces between tropocollagen protein chains. However, despite its abundance and possible usefulness in the medical field this complex physical system remains poorly understood to date. We present a theoretical study of the energetics of hydroxyapatite, its electronic, mechanical and thermodynamic properties. Our mechanical and thermodynamic properties from first principles are in excellent agreement with the rare available experimental data. The monoclinic and hexagonal phases are lowest in energy. A comparison of the phonon dispersions of these two phases reveals that a phase transition occurs due to a difference in vibrational free energy. The transition is of order-disorder type. Our calculated phase transition temperature is 680 K, in decent agreement with the experimentally determined 470 K. An alternative theoretical model yields 882 K. The phase transition is mediated by OH libration modes. We also report for the first time on a peculiarity in the phonon spectrum of hexagonal and monoclinic HA. When studying the Lyddane-Sachs-Teller shifts in the spectrum close to the [Gamma]-point we identify two vibration modes showing a systematically increasing Lyddane-Sachs-Teller shift in frequency with decreasing dielectric constant. In experiment, the dielectric constant varies between 5 and 20 depending on the Ca/P ratio in the sample. The frequency shifts in the affected modes are as large as 20 cm⁻¹ as one spans the range of the dielectric constant. Thus, a simple spectroscopic analysis of a sample of bone may determine the quality of the sample in a physiological sense. We also identify the chemically stable low energy surface configurations as function of the OH, PO₄ and Ca concentration. In the experimentally relevant OH-rich regime we find only two surfaces competing for lowest energy. The surface most stable over almost the entire OH-rich regime is OH-terminated, and is currently being investigated in the presence of water and atomic substitutions on the HA surface. / text

In electronic structure calculations the computational cost is of great importance because large systems can contain a huge number of electrons. One effective method to make such calculations is by density matrix purification. Although, the cost for this method is relatively low compared to other existing methods there is room for improvements. In this paper one method proposed by Emanuel Rubensson and one method proposed by Jaehoon Kim & Yousung Jung was compared to each other with respect to efficiency, simplicity and robustness. Both are improved methods to compute the density matrix by accelerated polynomial expansion. Rubensson’s method consists of two different algorithms and results showed that both performed better than Kim & Jung’s method in terms of efficiency, which is the property both methods directs their main focus on. The major differences between them was identified in terms of adaptivity. The methods require different inputs that demands separate levels of knowledge about the system. Kim & Jung’s method which require less knowledge can however benefit efficiency-wise from more information in order to optimize the algorithm for the system. Results also showed that both methods were stable, but since they only were tested with arbitrarily assumed input arguments no conclusion about their general stability could be drawn.

Quantum chemistry is plagued by the presence of high-rank quantities, stemming from the N-body nature of the electronic Schrödinger equation. These high-rank quantities present a significant mathematical and computational barrier to the computation of chemical observables, and also drastically complicate the pedagogical understanding of important interactions between particles in a molecular system. The application of physically-motivated rank reduction approaches can help address these to problems. This thesis details recent efforts to apply rank reduction techniques in both of these arenas. With regards to computational tractability, the representation of the 1/r Coulomb repulsion between electrons is a critical stage in the solution of the electronic Schrödinger equation. Typically, this interaction is encapsulated via the order-4 electron repulsion integral (ERI) tensor, which is a major bottleneck in terms of generation, manipulation, and storage. Many rank reduction techniques for the ERI tensor have been proposed to ameliorate this bottleneck, most notably including the order-3 density fitting (DF) and pseudospectral (PS) representations. Here we detail a new and uniquely powerful factorization - tensor hypercontraction (THC). THC decomposes the ERI tensor as a product of five order-2 matrices (the first wholly order-2 compression proposed for the ERI) and offers great flexibility for low-scaling algorithms for the manipulations of the ERI tensor underlying electronic structure theory. THC is shown to be physically-motivated, markedly accurate, and uniquely efficient for some of the most difficult operations encountered in modern quantum chemistry. On the front of chemical understanding of electronic structure theory, we present our recent work in developing robust two-body partitions for ab initio computations of intermolecular interactions. Noncovalent interactions are the critical and delicate forces which govern such important processes as drug-protein docking, enzyme function, crystal packing, and zeolite adsorption. These forces arise as weak residual interactions leftover after the binding of electrons and nuclei into molecule, and, as such, are extremely difficult to accurately quantify or systematically understand. Symmetry-adapted perturbation theory (SAPT) provides an excellent approach to rigorously compute the interaction energy in terms of the physically-motivated components of electrostatics, exchange, induction, and dispersion. For small intermolecular dimers, this breakdown provides great insight into the nature of noncovalent interactions. However, SAPT abstracts away considerable details about the N-body interactions between particles on the two monomers which give rise to the interaction energy components. In the work presented herein, we step back slightly and extract an effective 2-body interaction for each of the N-body SAPT terms, rather than immediately tracing all the way down to the order-0 interaction energy. This effective order-2 representation of the order-N SAPT interaction allows for the robust assignment of interaction energy contributions to pairs of atoms or functional groups (the A-SAPT or F-SAPT partitions), allowing one to discuss the interaction in terms of atom- or functional-group-pairwise interactions. These A-SAPT and F-SAPT partitions can provide deep insight into the origins of complicated noncovalent interactions, e.g., by clearly shedding light on the long-contested question of the nature of the substituent effect in substituted sandwich benzene dimers.

Electronic structure calculations of organic molecules are an important set of tools to gain understanding of molecular structures. This thesis presents two separate contributions to applying quantum chemistry to organic molecules. In the first section, the computational cost of a post-Hartree-Fock method is improved for large molecules by using graphical processing units. In this work, the resolution-of-the-identity second-order Møller-Plesset perturbation theory (RI-MP2) algorithm was adapted to send the large matrix multiplication steps to be run on a graphics co-processor. As a result, the calculations were performed up to 15x faster than a standard implementation for large molecules such as taxol. In the second section of the thesis, density functional theory is used to predict the molecular dipole moments of molecules that form self-assembled monolayers (SAMs) on metal surfaces. The dipole moment of the molecule that is aligned perpendicular to the surface in a SAM changes the work function of the surface. The calculated dipole moments correlate with the current density measured for the junctions by experimental collaborators. This result holds for a series of alkane chains with even and odd numbers of carbons and for molecules that have an amide group substituted for an ethylene unit. / Chemistry and Chemical Biology

published_or_final_version / Physics / Master / Master of Philosophy