Crystalline systems formed with transition metal elements tend to exhibit strong magneto-structural coupling that gives rise to unusual but exciting physical phenomena in these materials. In this dissertation, we present our findings from the studies of structural and physical properties of single phase compounds Co2MnSi, Ni16Mn6Si7 and Mn(Ni0.6Si0.4)2. In addition, the stability of a Ni2MnSi composition in a multiphase system is discussed by both theoretical and experimental approaches. All the works have been conducted with a focus on explaining the fundamental behaviors of these systems that have not been adequately addressed by other studies in the literature. We present an experimental and theoretical investigation of the half-metallic Heusler compound, Co2MnSi to address disorder occupancies and magnetic interactions in the material. Contrary to previous studies, our neutron diffraction refinement of the polycrystalline sample reveals almost identical amount of Mn and Co antisite disorders of ~6.5% and ~7.6%, respectively which is also supported explicitly by our first-principles calculations on the system with defects. A reduction of the net moment of Co2MnSi due to an antiferromagnetic interaction introduced by disordered Mn is observed by our theoretical study. The neutron refinements at 298 K, 100 K, and 4 K further supports such reduction of moments. The work also reports the growth of single crystal by the Czochralski method and determination of a Curie temperature of ~1014 K measured by both the electrical resistivity and dilatometry measurement. Studies of a Ni2MnSi Heusler system reveal two new systems i.e., the Ni16Mn6Si7 G-phase and the Mn(Ni0.6Si0.4)2 based Laves phase with complex crystal structures. These systems exhibit strong magneto-structural coupling that could lead to interesting physical behaviors. The lack of thorough understanding of the properties of these materials inspired us to undertake the present studies. We address the geometrically frustrated two-dimensional magnetic structure and spin canted weak ferromagnetic behavior of Ni16Mn6Si7. Our magnetization and specific heat measurements on a Czochralski grown single crystal sample depicts the paramagnetic to antiferromagnetic transition at 197 K, and a second phase change at 50 K. Furthermore, a gradual drop of zero field cooled magnetic susceptibility is observed below 6 K that is associated with the spin freezing effect. The neutron diffraction on the polycrystalline powder samples at the temperatures of interest reveals that the antiferromagnetism is governed by the magnetic ordering of the Mn ions in the octahedral network. Below the Néel temperature of 197 K, the 2/3 of Mn atom moments form a two-dimensional magnetic arrangement, while the 1/3 moments remain geometrically frustrated. The phase transition at 50 K is found to be associated with the reorientation of the 2D moments to a canted antiferromagnetic state and development of ordering of the frustrated paramagnetic ions. Magnetization measurements as a function of temperature and magnetic field in principal directions, permit to determine the anisotropic magnetic behavior of Ni16Mn6Si7 in terms of the magnetic structure obtained by the neutron diffraction measurements. We also report an irreversible smeared spin-flop type transition for the system at a higher magnetic field. The diffuse scattering due to the short-range ordering is a commonly occurring phenomenon in Laves phase materials. The occurrence of such distinct atomic arrangement can considerably influence the physical behavior of the material. Nevertheless, no structural reconstruction of such atomic distribution in Laves phase has ever been reported in the literature. In this work, we present the structural ordering, and the associated physical behavior of an antiferromagnetic Ni-Mn-Si Laves phase with a composition Mn(Ni0.6Si0.4)2. The possibility of unique short-range ordering in the material is first concluded based on our single crystal diffraction analysis. With the high-resolution transmission electron microscopy and electron energy loss spectroscopy analysis, our work resolves the distinct atomic ordering of the Laves phase system. The investigations reveal the origin of the short-range ordering to arise from a unique arrangement between Ni and Si. The study also presents the atomic resolution mapping of the Si atoms which has never been reported by any previous studies. With further electrical conductivity measurement, we find one of the consequences of the unique ordering reflected in a semiconducting like temperature dependence of the compound. The neutron diffraction at 298 K suggests Mn(Ni0.6Si0.4)2 to be a strong antiferromagnetic system, which is further supported by the successive magnetic susceptibility measurement. The Néel temperature is determined to be 550 K. We also address the stability of the hypothetical ferromagnetic Heusler compound Ni2MnSi which has been proposed to be a stable system by numerous theoretical studies. Our first-principles work corroborates those studies with a negative formation enthalpy of -1.46 eV/formula unit. However, after numerous attempts to synthesize the composition, we conclude that a single phase Heusler Ni2MnSi compound cannot form under ambient conditions. Our results show that the system crystallizes as a mixture of the two Ni-Mn-Si compounds, i.e., the Ni16Mn6Si7 type G-phase and Mn(Ni0.6Si0.4)2 based Laves phase. Our work provides a possible explanation for the unstable Ni2MnSi Heusler compound with the calculation of formation enthalpy of the hypothetical Heusler system in terms of the computed energies of the neighboring phases Ni16Mn6Si7 and Mn(Ni0.6Si0.4)2. / Thesis / Doctor of Philosophy (PhD)

在此論文中，我們利用第一原理計算研究多鐵材料Cu3Mo2O9的磁性、電子態及多鐵性質。我們發現在此系統中，電子與電子間的庫倫排斥力必須被考慮，以致於導帶與價帶間能隙能夠被良好地描述。由於晶體結構所導致的幾何不穩定性，系統的磁結構尚未在實驗測量中被確定。在我們的理論計算當中得到的磁結構與Vilminot等研究人員根據實驗結果猜測出的非線性反鐵磁結構類似。交換作用與自旋軌道耦合間的爭競決定了電子自旋方向的傾斜。計算所得到的交換作用係數與實驗結果吻合良好。利用Berry’s phase計算，我們得到了系統自發電極化的理論值，其強度與實驗量測值在同一個數量級。然而，在我們計算中得到的電極化方向(平行於b軸)與實驗(平行於c軸)不符。此外，我們發現一磁結構之理論電極化方向與實驗相符，然而其磁結構之對稱性與實驗不符。目前，尚未有第一原理計算研究此氧化物，我們希望此論文能夠對同樣有興趣研究此材料的研究人員有所幫助。 / In this thesis, we used the ab initio method to study a multiferroic oxide Cu3Mo2O9. The correlations of electrons must be considered in this system so that a reasonable energy gap can be obtained. Due to the geometric frustration of magnetic structure caused by crystal structure, the ground state spin configuration in this system still has not been determined experimentally. We found some spin configurations similar to the non-collinear anti-ferromagnetic spins configuration suggested by Vilminot et al.. Competition between exchange interactions and spin-orbit coupling effect determines the canting of spins on Cu atoms. The calculated exchange parameters agree with the experimental results well. By using Berry phase calculations, we obtained the theoretical value of spontaneous electric polarization. The strength of polarization in our results is in the same order of results of experiments. However, the direction of electric polarization we found (along b-axis) is different from the experimental measurements (along c-axis). We have found a spin configuration that the theoretical electric polarization of the state agrees with the experimental results. However, the symmetry of the spin configuration does not satisfy the conditions suggested by results of the neutron diffraction experiment. And, spins on neighboring Cu2 and Cu3 do not form a singlet dimer. Since there still is no ab initio calculation studying this oxide, we hope that our studies can help those who are also interested in this material.

No description available.

No description available.