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Recent experiments have shown that junctions consisting of individual single-molecule magnets (SMMs) bridged between two electrodes can be fabricated in three-terminal devices, and that the characteristic magnetic anisotropy of the SMMs can be affected by electrons tunneling through the molecule. Vibrational modes of the SMM can couple to electronic charge and spin degrees of freedom, and this coupling also influences the magnetic and transport properties of the SMM. The effect of electron-vibron coupling on transport has been extensively studied in small molecules, but not yet for junctions of SMMs. The goals of this thesis will be two-fold: to present a novel approach for studying the effects of this electron-vibron coupling on transport through SMMs that utilizes both density functional theory calculations and model Hamiltonian construction and analysis, and to present a software framework based on this hybrid approach for the simulation of transport across user-defined SMMs. The results of these simulations will indicate a characteristic suppression of the current at low energies that is strongly dependent on the overall electron-vibron coupling strength and number of molecular vibrational modes considered. / Master of Science

Di-n-propyl dicyanofumarate (DnPrDCF) and di-isopropyl dicyanofumarate (DiPrDCF) have been used as one-electron acceptors in the synthesis of charge-transfer salt magnets with decamethylmetallocenes, MCp*2 (M = Mn, Cr). Salts of each acceptor with each metallocene have been characterized and the structures of the chromium analogues have been solved. The two acceptors are structurally similar to dimethyl dicyanofumarate (DMeDCF) and diethyl dicyanofumarate (DEtDCF), which have been previously studied and found to form charge-transfer salt magnets with the aforementioned decamethylmetallocenes. A typical structural motif is present in these types of charge-transfer salts which allows for the comparison of magnetic properties based on the length or size of the alkyl group of the dialkyl dicyanofumarate. Some trends were established based on the magnetic properties of the homologous series including ordering temperature/bulkiness of the alkyl group and intrastack distances/theta values. Correlation of magnetic and structural properties may give some insight into "through-space" magnetic coupling, of which little is understood. / Master of Science

No description available.

This thesis will present the synthesis, characterization and magnetic measurements of lanthanide complexes with varying nuclearities (Ln, Ln2, Ln3 and Ln4). EuIII, GdIII, TbIII, DyIII, HoIII and YbIII have been selected as the metal centers. Eight polydentate Schiff-base ligands have been synthesized with N- and mostly O-based coordination environments which chelate 7-, 8- or 9-coordinate lanthanide ions. The molecular structures were characterized by single crystal X-ray crystallography and the magnetic properties were measured using a SQUID magnetometer. Each chapter consists of crystal structures and magnetic measurements for complexes with the same nuclearity. There are eight DyIII SMMs in this thesis which are discrete molecules that act as magnets below a certain temperature called their blocking temperature. This phenomenon results from an appreciable spin ground state (S) as well as negative uni-axial anisotropy (D), both present in lanthanide ions owing to their f electron shell, generating an effective energy barrier for the reversal of the magnetization (Ueff). The ab initio calculations are also included for the SMMs with high anisotropic energy barriers to understand the mechanisms of slow magnetic relaxation in these systems.

The magnetic properties of the (FexNi1-x)2B family of materials are explored using DFT calculations utilizing the FPLO and SPR-KKR code packages. It is found that a uniaxial magnetocrystalline anisotropy exists at around x = 0.8 with a magnetocrystalline anisotropy energy at around 0.3 MJ/m^3. A calculation of the lattice constant for these materials were attempted but failed due to the emergence of local minima and the calculations of magnetic properties were instead done using lattice parameters interpolated between known experimental values.

In traditional Permanent Magnet Machines, such as electric motors and generators, power is transmitted by magnetic flux passing through an air gap, which has a very low magnetic permeability, limiting performance. However, reducing the air gap through traditional means carries risks in manufacturing, with tight tolerances and associated costs, and reliability, with thermal and dynamic effects requiring adequate clearance. Using a magnetically permeable, high dielectric strength material has the potential to improve magnetic performance, while at the same time offering performance advantages in heat transfer. Ferrofluids were studied as a method for improved permeability in the rotor / stator gap with a combined experimental and computational approach. Results show promise for the ferrofluid technique. An off-the-shelf motor system showed improved performance with ferrofluids vs. fluids of equivalent viscosity, and improved performance vs. an air gap at low RPM. New generator designs showed design dependent performance gains, although some potential for negative performance effects. A proof of concept generator was built and tested, with increased voltage vs. RPM predicted through virtual prototyping, and validated through experimentation, showing ~10% improvement on voltage vs. RPM at the <600 RPM range. More repeatable engineering tests demonstrated a ~30% increase in the voltage / RPM relationship for designs with an isolated stator chamber and a large stator - rotor gap. However, the effects were negative for a similar system with a small stator-rotor gap due to leakage flux effects. New contributions to the body of knowledge in this area include: • Application of the ferrofluid technique to axial flux designs. • Development of a virtual prototype, including variations in the fluid viscosity due to ferrohydrodynamic effects. • Consideration of negative effects of ferrofluid immersion, such as shear losses and increases in leakage flux. • Optimization of the design to eliminate increased viscous losses. The improved design has been designed, built, and tested, featuring isolation of the ferrofluid from the rotating region. This offers all of the performance gain of improved magnetic permeability, while minimizing the offsetting losses from increased shear effects.

A skyrmion is a vortex-like spin pattern which has been observed in so-called B20 magnetic systems such as MnSi, (Mn,Fe)Si and a few other metallic magnets as well as in insulating Cu₂OSeO₃. We conduct a comprehensive study of muon spin relaxation (μSR) on bulk single crystals of MnSi and (Mn,Fe)Si, a MBE thin film of MnSi, and a ceramic specimen of Cu₂OSeO₃ in this work. The generic second-order like phase transition indicated by 1/T₁ peaks at T_c in bulk systems is discussed in light of the Brazovskii-type first-order phase transition due to the presence of the DM interaction. We also discuss the different temperature dependences of μ⁺ spin-lattice relaxation rate 1/T₁ in bulk pure systems MnSi and Cu₂OSeO₃ and their commonalities in the paramagnetic state and the ordered state due to the DM interaction. Furthermore, we highlight the enhanced 1/T₁ in the skyrmion crystal (SkX) phase compared to neighboring conical phases due to an abundance of low-energy magnetic fluctuations/excitations. This abundance is corroborated by the reduced static order parameter in the SkX phase of MnSi compared to neighboring conical phases, deduced by combining μSR experiments and magnetic field simulations. The intermediate (IM) region above T_c, where the modification of magnetic transition by the DM interaction starts to appear in MnSi, exhibit multi-time scale spin fluctuations, topologically non-trivial Hall resistivity and non-Fermi-liquid exponent of longitudinal resistivity in single-crystal Mn₀.₉Fe₀.₁Si and the MnSi MBE thin film, similar to the magnetically disordered phase of pure MnSi under hydrostatic pressure. These three defining features indicate a fluctuating skyrmion liquid in this magnetically ordered state, stabilized by pressure, disorder or reduced dimensionality. Moreover, the magnetic transition is strongly first order in the MnSi MBE thin film sample, different from the Brazovskii-type weakly first order transition in bulk samples, suggesting the importance of reduced dimensionality in modifying the nature of magnetic phase transitions in B20 systems.

A high-temperature, high-pressure autoclave has been adapted for use with a high-field nuclear magnetic resonance spectrometer. The autoclave has an internal pressure range of atmospheric pressure to 1.5 kbar and a temperature range of 273 K to 1900 K. The autoclave is usable in a high field (8 T) magnet with a room temperature, 76.4 mm bore. The autoclave was tested using assorted nuclear species with resonant frequencies ranging from 57 to 70 MHz at pressures ranging from atmospheric pressure to 1220 bar and temperatures ranging from 273 K to 448 K. Previously, the autoclave was used in conjunction with an iron magnet at temperatures to 1900 K and pressures to 1.5 kbar. / Graduation date: 1997

In this thesis we have developed electronic and spin model Hamiltonians to understand magnetism in molecule based magnets like photomagnets, high-nuclearity transition metal complexes and single molecule magnets. In chapter 1, we provide an overview of molecular magnets. Here, we present a survey on the literature available on molecule based magnets. The chapter throws light on various phenomena found in molecular magnetic systems that range in dimensions from 3D down to molecular dimension. This is followed by a brief introduction to high-nuclearity transition metal complexes and single molecule magnets (SMMs). In the last two sections of this chapter, we discuss Light Induced Excited Spin State Trapping (LIESST) and photomagnetism in some molecular systems. Chapter 2 discusses various theoretical models that have been developed for magnetism. We begin with an introduction to the spin Hamiltonian and the origin of direct and kinetic exchange in simple systems and extend it to larger systems. Then we introduce the concept of superexchange proposed by Goodenough and Kanamori, followed by introduction to anisotropic Dzyalashinskii-Moria (DM) exchange and Ruderman-Kittel-Kasuya-Yosida (RKKY) interactions. We also discuss molecular magnetic anisotropy, long-range magnetic interactions and higher order exchange interactions. These are effective model Hamiltonians that do not provide microscopic origin of magnetism, hence electronic model Hamiltonians need to be invoked. We introduce electronic model Hamiltonians like Huckel, Hubbard and Pariser-Parr-Popple (PPP) models and then present numerical techniques like valencebond (VB) and constant MS techniques that are used to exactly solve these model Hamiltonians. We present a many-body electronic model involving the active orbitals on the transition metal ions for photomagnetism in MoCu6 cluster, in chapter 3. The model is exactly solved using a valence bond approach. The ground state solution of the model is highly degenerate and is spanned by five S=0 states, nine S=1 states, five S=2 states and one S=3 state. The orbital occupancies in all these states correspond to six Cu(II) ions and one diamagnetic Mo(IV ) ion. The optically excited chargetransfer (CT) state in each spin sector occurs at nearly the same excitation energy of 2.993 eV for physically reasonable parameter values. We find that the excitation cross sections in different spin manifolds are similar in magnitude. The lifetime of the S=3 excited states is expected to be the largest as the number of states below that energy is very sparse in this spin sector compared to other spin sectors. This shows that photomagnetism is not due to preferential excitation to the S = 3 state. The inputs from the electronic model allows us to develop a kinetic model. In this model, photomagnetism is attributed to a long lived S=3 charge transfer excited state for which there appears to be sufficient experimental evidence. Based on this postulate, we model photomagnetism by including internal conversions and intersystem crossings. The key feature of the model is the assumption of existence of two kinds of S=3 states; one of which has no direct pathway for internal conversion and the other characterized by slow kinetics for internal conversion to the lowenergy states. The trapped S=3 state can decay via a thermally activated barrier to the other S = 3 state. The experimental XMT vs. T variation for two different irradiation times are fitted using Arrhenius dependence of the rate constants in the model. Conventional superexchange rules predict ferromagnetic exchange interaction between Ni(II) and M (M = MoV ,WV , NbIV ). Recent experiments show that in some systems this superexchange is antiferromagnetic. To understand this feature, in chapter 4 we develop a microscopic model for Ni(II) - M systems and solve it exactly using a valence bond approach. We identify direct exchange coupling, splitting of the magnetic orbitals and interorbital electron repulsions, on the M site as the parameters which control the ground state spin of various clusters of the Ni(II) - M system. We present quantum phase diagrams which delineate the high-spin and low-spin ground states in the parameter space. We fit the spin gap to a spin Hamiltonian and extract the effective exchange constant within the experimentally observed range, for reasonable parameter values. We also find a region in the parameter space where an intermediate spin state is the ground state. These results indicate that the spin spectrum of the microscopic model cannot be reproduced by a simple Heisenberg exchange Hamiltonian. The electronic model for A − B systems has been employed to reproduce the experimental magnetic data of the { NiW }2 system. In chapter 5, we present a theoretical approach to calculate the molecular magnetic anisotropy parameters, DM and EM for single molecule magnets in any eigenstate of the exchange Hamiltonian, treating the anisotropy Hamiltonian as a perturbation. Neglecting inter-site dipolar interactions, we calculate molecular magnetic anisotropy in a given total spin state from the known single-ion anisotropies of the transition metal centers. The method is applied to Mn12Ac and Fe8 in their ground and first few excited eigenstates, as an illustration. We have also studied the effect of orientation of local anisotropies on the molecular anisotropy in various eigenstates of the exchange Hamiltonian. We find that, in case of Mn12Ac, the molecular anisotropy depends strongly on the orientation of the local anisotropies and the spin of the state. The DM value of Mn12Ac is almost independent of the orientation of the local anisotropy of the core Mn(IV ) ions. In the case of Fe8, the dependence of molecular anisotropy on the spin of the state in question is weaker. We have also calculated the anisotropy constants for several sets of exchange parameters and find that in Mn12Ac the anisotropy increases with spin excitation gap while in Fe8, the anisotropy is almost independent of the gap. We have modeled the magnetic property of Nb6Ni12 cluster using a spin Hamiltonian in chapter 6. From Goodenough-Kanamori rules we should expect a ferromagnetic exchange between Nb and Ni ions. However, the magnetic studies indicate that the interaction is antiferromagnetic. We give reasons for the anomaly and fit the XMT data using an antiferromagnetic Heisenberg model. The observed XMT value at 2 K however does not correspond to ferrimagnetic ground state of Stot=9 and we invoke intermolecular interaction to explain this feature.