Rozprawy doktorskie na temat „Solid State Physics - Crystalline Order”

The work presented in this thesis is a topological approach for understanding the formation of structures from the liquid state. The strong difference in the thermal transport properties of non- crystalline solid states as compared to crystalline counterparts is considered within this topological framework. Herein, orientational order in undercooled atomic liquids, and derivative solid states, is identified with a quaternion order parameter.

In light of the four-dimensional nature of quaternion numbers, spontaneous symmetry breaking from a symmetric high-temperature phase to a low-temperature phase that is globally orientationally ordered by a quaternion order parameter is forbidden in three- and four-dimensions. This is a higher-dimensional realization of the Mermin-Wagner theorem, which states that continuous symmetries cannot be spontaneously broken at finite temperatures in two- and one-dimensions.

Understanding the possible low-temperature ordered states that may exist in these scenarios (of restricted dimensions) has remained an important problem in condensed matter physics. In approaching a topological description of solidification in three-dimensions, as characterized by a quaternion orientational order parameter, it is instructive to first consider the process of quaternion orientational ordering in four-dimensions. This 4D system is a direct higher-dimensional analogue to planar models of complex n–vector ( n = 2) ordered systems, known as Josephson junction arrays.

Just as Josephson junction arrays may be described mathematically using a lattice quantum rotor model with O(2) symmetry, so too can 4D quaternion n–vector (n = 4) ordered systems be modeled using a lattice quantum rotor model with O(4) symmetry. O(n) quantum rotor models (that apply to n–vector ordered systems that exist in restricted dimensions) include kinetic and potential energy terms. It is the inclusion of the kinetic energy term that leads to the possible realization of two distinct ground states, because the potential and kinetic energy terms cannot be minimized simultaneously.

The potential energy term is minimized by the total alignment of O(n) rotors in the ground state, such that it is perfectly orientationally ordered and free of topological defects. On the other hand, minimization of the kinetic energy term favors a low-temperature state in which rotors throughout the system are maximally orientationally disordered.

In four-dimensions, the O(4) quantum rotor model may be used to describe a 4D plastic crystal that forms below the melting temperature. A plastic crystal is a mesomorphic state of matter between the liquid and solid states. The realization of distinct low-temperature states in four-dimensions, that are orientationally-ordered and orientationally-disordered, is compared with the realization of phase-coherent and phase-incoherent low-temperature states of O(2) Josephson junction arrays. Such planar arrays have been studied extensively as systems that demonstrate a topological ordering transition, of the Berezinskii-Kosterlitz-Thouless (BKT) type, that allows for the development of a low-temperature phase-coherent state.

In O(2) Josephson junction arrays, this topological ordering transition occurs within a gas of misorientational fluctuations in the form of topological point defects that belong to the fundamental homotopy group of the complex order parameter manifold (S¹). In this thesis, the role that an analogous topological ordering transition of third homotopy group point defects in a four-dimensional O(4) quantum rotor model plays in solidification is investigated. Numerical Monte-Carlo simulations, of the four-dimensional O(4) quantum rotor model, provide evidence for the existence of this novel topological ordering transition of third homotopy group point defects.

A non-thermal transition between crystalline and non-crystalline solid ground states is considered to exist as the ratio of importance of kinetic and potential energy terms of the O(4) Hamiltonian is varied. In the range of dominant potential energy, with finite kinetic energy effects, topologically close-packed crystalline phases develop for which geometrical frustration forces a periodic arrangement of topological defects into the ground state (major skeleton network). In contrast, in the range of dominant kinetic energy, orientational disorder is frozen in at the glass transition temperature such that frustration induced topological defects are not well-ordered in the solid state.

Ultimately, the inverse temperature dependence of the thermal conductivity of crystalline and non-crystalline solid states that form from the undercooled atomic liquid is considered to be a con- sequence of the existence of a singularity at the point at which the potential and kinetic energy terms become comparable. This material transport property is viewed in analogue to the electrical transport properties of charged O(2) Josephson junction arrays, which likewise exhibit a singularity at a non-thermal phase transition between phase-coherent and phase-incoherent ground states.

In this Thesis, systems of confined and flexoelectric liquid crystal systems have been studied using molecular computer simulations. The aim of this work was to provide a molecular model of a bistable display cell in which switching is induced through the application of directional electric field pulses. In the first part of this Thesis, the study of confined systems of liquid crystalline particles has been addressed. Computation of the anchoring phase diagrams for three different surface interaction models showed that the hard needle wall and rod-surface potentials induce both planar and homeotropic alignment separated by a bistability region, this being stronger and wider for the rod-surface varant. The results obtained using the rod-sphere surface model, in contrast, showed that tilted surface arrangements can be induced by surface absorption mechanisms. Equivalent studies of hybrid anchored systems showed that a bend director structure can be obtained in a slab with monostable homeotropic anchoring at the top surface and bistable anchoring at the bottom, provided that the slab height is sufficiently large and the top homeotropic anchoring is not too strong. In the second part of the Thesis, the development of models for tapered (pear-shaped) mesogens has been addressed. The first model considered, the truncated Stone expansion model, proved to be unsuccessful in that it did not display liquid crystalline phases. This drawback was then overcome using the alternative parametric hard Gaussian overlap model which was found to display a much richer phase behaviour. With a molecular elongation k = 5, both nematic and interdig-itated smectic A2 phases were obtained. In the final part of this Thesis, the knowledge acquired from the two previous studies was united in an attempt to model a bistable display cell. Switching between the hybrid aligned nematic and vertical states of the cell was successfully performed using pear shaped particles with both dielectric and dipolar couplings to an applied field. Also, a parameter window was identified, for values of the electric field, dielectric susceptibility and dipole moment, for which directional switching is achievable between the bistable states.

This thesis describes the development and testing of a new technique for the measurement of structure factors based on the matching of theoretical calculations with experimental, energy-filtered zone-axis Convergent Beam Electron Diffraction (CBED) patterns. The sum-of-squares difference between a set of experimental diffraction intensities and a theoretical calculation is minimised by varying a set of low-order structure factors until a best fit is obtained. The basic theory required for the simulation of zone-axis CBED patterns is given. Additional theory is developed specifically for the pattern matching method in order to improve the efficiency of the matching calculation. This includes the development of analytic expressions for the gradient of the sum-of-squares with respect to each of the fitting parameters, and the addition of beams to the pattern calculation by second-order perturbation theory. The effects of random and systematic errors are considered by fitting to simulated `noisy' data. A wide range of potential systematic error effects are investigated and limits are found for errors in the accelerating voltage, Debye-Waller factor and lattice parameter which reduce systematic errors to acceptable levels. These tests also investigate the sensitivity of the method to structure factor variations, which gives an indication of how many structure factors can be measured. Finally, the method is applied to the measurement of low-order structure factors from experimental Si [110] zone-axis patterns. The results are compared to the best X-ray Pendellösung measurements available, and the bonding charge densities obtained from both the zone-axis and X-ray measurements are constructed

Solid state materials are candidates to exhibit a large field-driven thermal response in the vicinity of first-order transitions. The strong sensitivity of the transition temperature with the applied field and the latent heat associated with the change of phase can give rise to the giant magneto-, electro-, baro-, and elastocaloric effects. Furthermore, the coupling between structural, magnetic and electronic degrees of freedom at the transition regime enables the thermal response to be driven by multiple fields and, thus, giving rise to the multicaloric effect. In the last years, the interest in understanding and tailoring novel caloric materials has exceptionally grown in view of their potential application to alternative cooling technologies for large scale industry. The present thesis reports the giant caloric effects encompassing the Fe49Rh51 magnetovolumic transition, the magnetostructural martensitic transformation in Ni-Mn based Heusler alloys, and the ferroelectric perovskites BaTiO3 and Pb(Sc0.5Ta0.5)O3. The physical conditions for the optimization of the thermal response which yield to an enlarged magnitude and operation range are explored, as well as the corresponding reproducibility upon field cycling and the potential multicaloric character. This evaluation is achieved by means of a complete caloric characterization in which the calorimetric experimental techniques which have been developed in purpose are crucial.
Els materials d'estat sòlid són susceptibles de mostrar una gran resposta tèrmica induïda per un camp extern a l'entorn de transicions de fase de primer ordre. La forta sensitivitat de la temperatura de transició amb el camp aplicat i la calor latent associada amb el canvi de fase poden donar lloc als efectes magneto-, electro-, baro- i elastocalòric gegants. A més, l'acoblament entre els graus de llibertat estructurals, magnètics i electrònics en el règim de transició possibilita que la resposta tèrmica sigui induïda per múltiples camps, originant així l'efecte multicalòric. En els darrers anys, l'interès en entendre i elaborar materials calòrics ha crescut excepcionalment, amb l'ull posat en les aplicacions potencials en tecnologies de refrigeració alternatives per a la indústria a gran escala. La present tesi reporta els efectes calòrics gegants que acompanyen la transició magnetovolúmica del Fe49Rh51, la transformació martensítica en aliatges Heusler amb base de Ni-Mn, i les perovskites ferroelèctriques de BaTiO3 i de Pb(Sc0.5Ta0.5)O3. S'exploren les condicions físiques propícies per a una optimització de la resposta tèrmica que resulten amb un eixamplament en magnitud i en rang d'operació, així com també la reproducibilitat corresponent sota ciclatge i el potencial caràcter multicalòric. Aquesta avaluació s'aconsegueix per mitjà d'una caracterització calòrica completa en què les tècniques experimentals calorimètriques que s'han desenvolupat amb aquest propòsit són crucials

Orientadores: Peter A. B. Schulz, John T. Chalker
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin
Made available in DSpace on 2018-08-06T19:00:22Z (GMT). No. of bitstreams: 1 Pereira_AnaLuizaCardoso_D.pdf: 2880300 bytes, checksum: ffd133973b4bc6e23c91694bc47d8794 (MD5) Previous issue date: 2005
Resumo: Esse trabalho é dedicado ao estudo de dois problemas de interesse atual em sistemas quânticos de baixa dimensionalidade. Ambos são relacionados ao processo de localização eletrônica no regime Hall quântico. O primeiro problema diz respeito ao destino dos estados estendidos no limite de baixos campos magnéticos ou forte desordem, onde ocorre a transição de líquido de Hall para o isolante de Hall. O problema é abordado através de simulações numéricas, com um modelo de rede bidimensional tratado por um Hamiltoniano tight-binding, considerando-se tanto desordem tipo ruído branco quanto desordem correlacionada com perfil Gaussiano. Nós observamos que à medida que o campo magnético tende a zero ou a desordem é suficientemente aumentada no sistema, os estados estendidos sofrem um deslocamento em relação ao centro das bandas de Landau, indo em direção às mais altas energias e, eventualmente, ultrapassando a energia de Fermi. Esse mecanismo é chamado na literatura de levitação de estados estendidos. Nossos resultados permitem uma análise quantitativa. Identificamos os seguintes parâmetros como sendo os relevantes para mapear a levitação: (i) a razão entre escalas de energia ¿ entre a energia de separação dos níveis de Landau e o alargamento do nível devido à desordem; e (ii) a razão entre escalas de comprimento ¿ entre o comprimento magnético e o comprimento de correlação da desordem. Analisando uma vasta gama de parâmetros, uma expressão de escala descrevendo a levitação de estados estendidos é estabelecida neste trabalho. O segundo problema abordado nesta tese é relacionado ao processo de blindagem do potencial de desordem e ao mecanismo de formação dos estados localizados em sistemas Hall quânticos. O trabalho analítico apresentado aqui é motivado por recentes resultados experimentais, que mostram imagens de microscopia com medidas locais do potencial eletrostático e da compressibilidade desses sistemas, evidenciando como se dá o processo de carga de estados localizados por cargas inteiras ou fracionárias (quase-partículas). Em um regime onde o comportamento é dominado por interações Coulombianas, estabelecemos um modelo eletrostático que descreve o estado localizado como sendo uma região compressível (quantum dot ou antidot) envolta por um plano incompressível, usando a aproximação de Thomas-Fermi para tratar as interações. O potencial eletrostático nas vizinhanças da região compressível é calculado, fornecendo o tamanho dos saltos que ocorrem no potencial à medida que cada carga é adicionada ou removida do estado localizado. Além de mostrar como estes saltos se tornam menores com o aumento do índice de Landau, nossos resultados mostram a dependência deles com a altura de observação do potencial (ou seja, a altura da ponta de prova em relação ao gás de elétrons). O modelo apresentado pode ser usado para tratar estados localizados observados nos platôs do efeito Hall quântico inteiro ou fracionário
Abstract: This work is devoted to the study of two problems of current interest in low dimensional quantum systems. Both are related to the process of electron localization in the quantum Hall regime. The first problem refers to the fate of extended states in the limit of low magnetic fields or strong disorder, where the transition from quantum Hall liquid to Hall insulator takes place. A numerical approach to the problem is used, with a 2D lattice model treated in a tight-binding framework, considering both white-noise and Gaussian correlated disorder. We observe that as the magnetic field vanishes or the disorder is sufficiently increased in the system, the extended states are shifted from the Landau band centers, going to higher energies and, eventually, rising above the Fermi energy. This mechanism is referred in the literature as levitation of extended states. Our results allow a quantitative analysis. We identify the following parameters as the relevant ones to map the levitation: (i) the energy scales ratio - between the energy separation of consecutive Landau levels and the level broadening due to disorder; and (ii) the length scales ratio - between the magnetic length and the disorder correlation length. Analyzing a wide range of parameters, a scaling expression describing the levitation of extended states is established. The second problem considered in this thesis is related to the screening of the disorder potential and to the mechanism of formation of localized states in quantum Hall systems. The analytical work we present here is motivated by recent imaging experiments, which probe locally the electrostatic potential and the compressibility of these systems, showing the charging of individual localized states by integer or fractional charges (quasiparticles). For a regime where the behavior is dominated by Coulomb interactions, we set out an electrostatic model describing the localized state as a compressible region (quantum dot or antidot) embebed in an incompressible background, using the Thomas-Fermi approximation to treat the interactions. The electrostatic potential in the vicinity of the compressible region is calculated, providing the size of potential steps as each charge is added or removed from the localized state. Besides from showing how the potential steps get smaller for higher Landau levels, our results show the dependence of these steps with the height of observation (i.e., the distance from the scanning probe to the electron gas). The proposed model can be used to treat localized states observed on integer or fractional quantum Hall plateaus
Doutorado
Física da Matéria Condensada
Doutor em Ciências

Long range order (LRO) is one of the most important properties of physics systems, especially for a strongly correlated system. In this thesis, the long range order in a few strongly correlated systems is investigated both rigorously and numerically.
Magnetic orders in the two-dimensional periodic Anderson model (PAM) were investigated in the project. Several numerical methods including exact diagonalization, mean field methods and the constrained path Monte Carlo (CPMC) method were used here. We studied the effect of the dispersion of the impurity band on the magnetism and gave estimated phase diagrams on the band filling and impurity chemical potential plane, by comparing the ground state energies and by studying the Fourier transformation of the spin-spin correlations.
The Neel long range order in various quantum spin models was studied. A spatially anisotropy antiferromagnetic Heisenberg system was studied and a critical point Jup⊥S was obtained. When J⊥ is larger than Jup⊥S , the Neel long range order was proved to exist in the ground state of the system. Then an onsite single-ion anisotropy D-term was imposed on the above system and its effect on the existence of the long range order was studied. We obtained a critical line on the DJ⊥ plane such that above which the long range order exists. To get insight into the long range order in the two-dimensional isotropic Heisenberg model, the XXZ model and the Heisenberg system with next nearest neighbors interaction were studied. For the XXZ model, two critical couplings DeltaXY and DeltaIsing were obtained such that when 0 ≤ Delta ≤XY or Delta ≥ DeltaIsing, the Neel order appears. For the antiferromagnetic Heisenberg model with next nearest neighbors interaction both spin S = 1/2 and S = 1 were studied. For S = 1/2, a critical next nearest neighbors ferro-coupling Jc2 was obtained such that when J2 ≤ Jc2 , the Neel long range order appears, while for S = 1 an improved Jc2 was obtained such that when J2 ≤ Jc2 the Neel order still exists even with frustration.
Wang Yongqiang = 强关联系统中的长程序 / 王永强.
"June 2005."
Adviser: Haiqing Lin.
Source: Dissertation Abstracts International, Volume: 67-07, Section: B, page: 3861.
Thesis (Ph.D.)--Chinese University of Hong Kong, 2005.
Includes bibliographical references (p. 156-162).
Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Text in English; abstracts in English and Chinese.
School code: 1307.
Wang Yongqiang = Qiang guan lian xi tong zhong de chang cheng xu / Wang Yongqiang.

Diffusion plays an important role in a number of processes like heterogeneous catalysis, corrosion, separation and purification of chemicals of industrial importance, steel hardening, fuel cells, and solid electrolytes for batteries. It also plays a vital role in several biological processes like transport across biomembranes, nerve impulse, flow of blood and permeation of ingested drug. The elementary process of diffusion in solids is quite different from those in liquids. Similarly, the mode of diffusion in porous solid where different regimes such Knudsen regime exists bears little similarity to those in a dense close-packed crystalline solid. Chapter 1 provides a brief introduction to basics of diffusion in different phases of condensed matter. Among the various phases discussed are liquids, close-packed crystalline solids (e.g., body-centered cubic solids), amorphous solids (e.g. glasses) and microporous crystalline solids (e.g., zeolites). Diffusion in these widely differing phases often bears no resemblance to each other; the rate of diffusion in these phases varies over many orders of magnitude and the elementary step and mechanism in the diffusion process are very different. Brief introduction to theories for diffusion in these phases is provided. Various experimental techniques to measure diffusivities are discussed. Different microscopic models to explain the Quasi Elastic Neutron Scattering (QENS) spectra of these phases yield an insight into the elementary step of the diffusion process. Notwithstanding the fact that completely different models are invoked to explain diffusion in different phases, there are certain underlying generic behaviour across these widely differing phases as the recent work on size dependence of diffusion in these phases demonstrate. Diffusion of a molecule or species (in the context of diffusion within condensed phases) without loss of generality may be said to occur in a medium. A universal behaviour observed is that self diffusivity exhibits a maximum as a function of the size of the diffusant when the diffusant is confined to a medium, as a result of what is known as the Levitation Effect. Such a maximum in self diffusivity has been seen in widely differing medium: microporous solids, dense liquids, ions in polar solvents, etc. The aim of the thesis is to investigate and further explore such universal behaviour and demonstrate for the first time the existence of common trends across different condensed phases in spite of difference in the detail at the microscopic level. In Chapter 2, we report a molecular dynamics study of diffusion of diatomic species AB within zeolite Y. The bond length of A-B as well as the interaction of A and B with the host zeolite atoms are varied. The results demonstrate that for the symmetric case (when A=B or AA), there exists a preferred bond length (determined by the bottleneck or window diameter) when the diffusivity is maximum. This is in agreement with previous results on monatomic species which also exhibit a similar diffusivity maximum. More importantly, no such maximum is seen when the interaction asymmetric is introduced in AB. Slight asymmetry in the interaction gives rise to a weak maximum while large asymmetry in interaction obliterates the diffusivity maximum. These results suggest that the importance of interaction between the diffusant and the medium in Levitation Effect or size-dependent diffusivity maximum. Further, it also demonstrates for the first time the close association between an inversion centre (in a statistical sense and not in the crystallographic sense) and the Levitation Effect. In Chapter 3, a study of size dependence of solutes in a Lennard-Jones liquid is reported. Einstein and others derived the reciprocal dependence of the self-diffusivity D on the solute radius ru for large solutes based on kinetic theory. We examine here (a) the range of ru over which Stokes-Einstein (SE) dependence is valid and (b) the precise dependence for small solutes outside of the SE regime. We show through molecular dynamics simulations that there are two distinct regimes for smaller solutes: (i) the interaction or Levitation Effect (LE) regime for solutes of intermediate sizes and (ii) the D 1/ru2 for still smaller solutes. We show that as the solute-solvent size ratio decreases, the breakdown in the Stokes-Einstein relationship leading to the LE regime has its origin in dispersion interaction between the solute and the solvent. These results explain reports of enhanced solute diffusion in solvents existing in the literature seen for small solutes for which no explanation exists. Several properties have been computed to understand the nature of solute motion in different regimes. We investigate in Chapter 4, the dependence of self diffusivity on the size of the diffusant in a disordered medium with the objective of understanding the experimentally observed correlation between self diffusivity and activation energy seen in a wide variety of glasses. Typically, it is found in many ionic glasses that a higher conductivity is associated with lower activation energy and vice versa. Our understanding of transport in glasses as provided by existing theories does not offer an explanation of this correlation. We have carried out molecular dynamics simulation as a function of the size of the impurity atom or diffusant (both neutral and charged) in a model host amorphous matrix. We find that there is a maximum in self diffusivity as a function of the size of the impurity atom suggesting that there is an appropriate size for which the diffusivity is maximum. The activation energy is found to be the lowest for this size of the impurity. A similar maximum has previously been found in other condensed phases such as confined fluids and dense liquids and has its origin in the Levitation Effect. The implications of this result for understanding ionic conductivity in glasses are discussed. Our result suggests that there is a relation between microscopic structure of the amorphous solid, diffusivity or conductivity and activation energy. The nature of this relationship is discussed in terms of the Levitation parameter showing that diffusivity is maximum when the size of the neck or doorway radius is comparable with the size of the diffusant. Our computational results here are in excellent agreement with independent experimental results which show that structural features of the glass are important in determining the ionic conductivity. In Chapter 5, we report results of molecular dynamics investigations into neutral impurity diffusing within an amorphous solid as a function of the size of the diffusant and density of the host amorphous matrix. We find that self diffusivity exhibits an anomalous maximum as a function of the size of the impurity species. An analysis of properties of the impurity atom with maximum diffusivity shows that it is associated with lower mean square force, reduced backscattering of velocity autocorrelation function, near-exponential decay of the intermediate scattering function (as compared to stretched-exponential decay for other sizes of the impurity species) and lower activation energy. These results demonstrate the existence of well known size-dependent diffusivity maximum in disordered solids. Further, we show that the diffusivity maximum is observed at lower impurity diameters with increase in density. This is explained in terms of the levitation parameter and the void structure of the amorphous solid. We demonstrate that these results imply contrasting dependence of self diffusivity (D) on the density of the amorphous matrix, . D increases with  for small sizes of the impurity but shows an increase followed by a decrease for intermediate sizes of the impurity atom. For large sizes of the impurity atom, D decreases with increase in . These contrasting dependence arises naturally from the existence of Levitation Effect. In Chapter 6, we discuss size dependence of impurity diffusion in an ordered system. We report molecular dynamics simulation studies to understand the role of impurity size and impurity-host interaction on impurity diffusivity in a body centered cubic solid. The simulation studies have been performed for a set of impurity-host interaction parameter ih (i=impurity, h=host atom) for a range of impurity sizes in rigid and flexible bcc solids. A double maximum is seen corresponding to two different sizes of the impurity species. Anomalous maximum is seen for a larger size of the impurity species in the case of the rigid host as compared to flexible host. The second anomalous diffusivity disappears with decrease in ih in flexible bcc solid. For one of the ih where double diffusivity maxima are observed, various properties are analysed to understand the anomalous diffusion behaviour. The impurity with anomalous diffusion has lower activation energy as compared to other impurities. Among the two anomalous impurities, the impurity with higher diffusivity has lower activation energy. The anomalous regime impurities as associated with velocity autocorrelation function with little or no backscattering, minimum average mean square force due to host atoms, lower activation energy. The self intermediate scattering function shows faster decay and a single relaxation time for anomalous regime impurity and two relaxation times for other impurity sizes. The wavenumber dependence of diffusivity of impurities shows oscillatory behaviour except for the anomalous regime impurities which show monotonic dependence on wavenumber. Chapter 7 discusses the influence of temperature induced solid-liquid phase transition on the size-dependent diffusivity. We report results for two distinct cases: (a) when the phase change is associated with corresponding changes in density and (b) when the phase change occurs at constant density. The latter is carried out so as to obtain the influence of disorder on the size-dependent diffusion or Levitation Effect. Studies with variable density are useful to understand the effect of disorder as well as change in density on size-dependent diffusivity. Two diffusivity maxima in the solid face-centred cubic phase is seen when the impurity-medium interaction is sufficiently large. One of these diffusivity maximum disappears with decrease in h. The impurities near the diffusivity maximum show velocity autocorrelation function with little backscattering, minimum in the average mean square force, lower activation energy, faster decay of self intermediate scattering function with a single relaxation time and a monotonic decay in wavevector dependence of diffusivity. Chapter 8 reports molecular dynamics simulations of a model guest tetrahedral molecule AX4 with differing bond lengths lAX have been carried out in a sphere with different surface roughness. The rotational-diffusion coefficient Dr shows a maximum for a particular value of lAX. This corresponds to the distance at which the interaction of the guest with the atoms of the host is most favourable. Although, the intensity of the maximum decreases with increase in the roughness of the confining surface, it is seen that the maximum exists even for a reasonably high degree of roughness. The observed maximum arises from the minimum in the torque on the tetrahedral molecule from its interaction with the confining medium due to mutual cancellation of forces. Activation energy for rotation is seen to be also a minimum for the bond length for which Dr is a maximum. These results suggest that there is a maximum in the rotational-diffusion coefficient when the rotating molecule is confined to a sphere of comparable size similar to the maximum in translational diffusion coefficient seen in porous solids and known as the Levitation Effect. On increase in the roughness of the sphere surface, the value of lAX at which the maximum in Dr is seen decreases. This is similar to the shift seen in the size of the diffusant corresponding to maximum diffusivity in the case of translational diffusivity. In Chapter 9 possible extensions to the work reported in the previous chapters and the directions to take are discussed. Symmetry plays an important role in size dependent diffusivity maximum in microporous crystalline solids; it would be interesting to investigate if similar role of symmetry exists in case of liquids and other disordered solids. Previous work from this laboratory on ions in water has shown the importance of electrostatic interactions. In the light of this, it would be interesting to see the influence of long-range interactions in breakdown of Stokes-Einstein relationship in liquids. Effect of density of the medium on impurity diffusion can be studied over a wide range of densities in case of supercritical fluids such as ions in water (where electrostatic interactions are present) and these can provide greater insight into dependence of diffusion on density. The origin of two diffusivity maxima in case of body-centered and face-centred cubic solids needs a detailed investigation to understand its origin. Quantification of disorder and its effect on size dependence of diffusion would be of interest. A detailed comparison with experimental data of matrix isolated molecules to understand and verify the dependence of rotational diffusivity on the size of the molecule as well as the cavity radius would be instructive.

Diffusion plays an important role in a number of processes like heterogeneous catalysis, corrosion, separation and purification of chemicals of industrial importance, steel hardening, fuel cells, and solid electrolytes for batteries. It also plays a vital role in several biological processes like transport across biomembranes, nerve impulse, flow of blood and permeation of ingested drug. The elementary process of diffusion in solids is quite different from those in liquids. Similarly, the mode of diffusion in porous solid where different regimes such Knudsen regime exists bears little similarity to those in a dense close-packed crystalline solid. Chapter 1 provides a brief introduction to basics of diffusion in different phases of condensed matter. Among the various phases discussed are liquids, close-packed crystalline solids (e.g., body-centered cubic solids), amorphous solids (e.g. glasses) and microporous crystalline solids (e.g., zeolites). Diffusion in these widely differing phases often bears no resemblance to each other; the rate of diffusion in these phases varies over many orders of magnitude and the elementary step and mechanism in the diffusion process are very different. Brief introduction to theories for diffusion in these phases is provided. Various experimental techniques to measure diffusivities are discussed. Different microscopic models to explain the Quasi Elastic Neutron Scattering (QENS) spectra of these phases yield an insight into the elementary step of the diffusion process. Notwithstanding the fact that completely different models are invoked to explain diffusion in different phases, there are certain underlying generic behaviour across these widely differing phases as the recent work on size dependence of diffusion in these phases demonstrate. Diffusion of a molecule or species (in the context of diffusion within condensed phases) without loss of generality may be said to occur in a medium. A universal behaviour observed is that self diffusivity exhibits a maximum as a function of the size of the diffusant when the diffusant is confined to a medium, as a result of what is known as the Levitation Effect. Such a maximum in self diffusivity has been seen in widely differing medium: microporous solids, dense liquids, ions in polar solvents, etc. The aim of the thesis is to investigate and further explore such universal behaviour and demonstrate for the first time the existence of common trends across different condensed phases in spite of difference in the detail at the microscopic level. In Chapter 2, we report a molecular dynamics study of diffusion of diatomic species AB within zeolite Y. The bond length of A-B as well as the interaction of A and B with the host zeolite atoms are varied. The results demonstrate that for the symmetric case (when A=B or AA), there exists a preferred bond length (determined by the bottleneck or window diameter) when the diffusivity is maximum. This is in agreement with previous results on monatomic species which also exhibit a similar diffusivity maximum. More importantly, no such maximum is seen when the interaction asymmetric is introduced in AB. Slight asymmetry in the interaction gives rise to a weak maximum while large asymmetry in interaction obliterates the diffusivity maximum. These results suggest that the importance of interaction between the diffusant and the medium in Levitation Effect or size-dependent diffusivity maximum. Further, it also demonstrates for the first time the close association between an inversion centre (in a statistical sense and not in the crystallographic sense) and the Levitation Effect. In Chapter 3, a study of size dependence of solutes in a Lennard-Jones liquid is reported. Einstein and others derived the reciprocal dependence of the self-diffusivity D on the solute radius ru for large solutes based on kinetic theory. We examine here (a) the range of ru over which Stokes-Einstein (SE) dependence is valid and (b) the precise dependence for small solutes outside of the SE regime. We show through molecular dynamics simulations that there are two distinct regimes for smaller solutes: (i) the interaction or Levitation Effect (LE) regime for solutes of intermediate sizes and (ii) the D 1/ru2 for still smaller solutes. We show that as the solute-solvent size ratio decreases, the breakdown in the Stokes-Einstein relationship leading to the LE regime has its origin in dispersion interaction between the solute and the solvent. These results explain reports of enhanced solute diffusion in solvents existing in the literature seen for small solutes for which no explanation exists. Several properties have been computed to understand the nature of solute motion in different regimes. We investigate in Chapter 4, the dependence of self diffusivity on the size of the diffusant in a disordered medium with the objective of understanding the experimentally observed correlation between self diffusivity and activation energy seen in a wide variety of glasses. Typically, it is found in many ionic glasses that a higher conductivity is associated with lower activation energy and vice versa. Our understanding of transport in glasses as provided by existing theories does not offer an explanation of this correlation. We have carried out molecular dynamics simulation as a function of the size of the impurity atom or diffusant (both neutral and charged) in a model host amorphous matrix. We find that there is a maximum in self diffusivity as a function of the size of the impurity atom suggesting that there is an appropriate size for which the diffusivity is maximum. The activation energy is found to be the lowest for this size of the impurity. A similar maximum has previously been found in other condensed phases such as confined fluids and dense liquids and has its origin in the Levitation Effect. The implications of this result for understanding ionic conductivity in glasses are discussed. Our result suggests that there is a relation between microscopic structure of the amorphous solid, diffusivity or conductivity and activation energy. The nature of this relationship is discussed in terms of the Levitation parameter showing that diffusivity is maximum when the size of the neck or doorway radius is comparable with the size of the diffusant. Our computational results here are in excellent agreement with independent experimental results which show that structural features of the glass are important in determining the ionic conductivity. In Chapter 5, we report results of molecular dynamics investigations into neutral impurity diffusing within an amorphous solid as a function of the size of the diffusant and density of the host amorphous matrix. We find that self diffusivity exhibits an anomalous maximum as a function of the size of the impurity species. An analysis of properties of the impurity atom with maximum diffusivity shows that it is associated with lower mean square force, reduced backscattering of velocity autocorrelation function, near-exponential decay of the intermediate scattering function (as compared to stretched-exponential decay for other sizes of the impurity species) and lower activation energy. These results demonstrate the existence of well known size-dependent diffusivity maximum in disordered solids. Further, we show that the diffusivity maximum is observed at lower impurity diameters with increase in density. This is explained in terms of the levitation parameter and the void structure of the amorphous solid. We demonstrate that these results imply contrasting dependence of self diffusivity (D) on the density of the amorphous matrix, . D increases with  for small sizes of the impurity but shows an increase followed by a decrease for intermediate sizes of the impurity atom. For large sizes of the impurity atom, D decreases with increase in . These contrasting dependence arises naturally from the existence of Levitation Effect. In Chapter 6, we discuss size dependence of impurity diffusion in an ordered system. We report molecular dynamics simulation studies to understand the role of impurity size and impurity-host interaction on impurity diffusivity in a body centered cubic solid. The simulation studies have been performed for a set of impurity-host interaction parameter ih (i=impurity, h=host atom) for a range of impurity sizes in rigid and flexible bcc solids. A double maximum is seen corresponding to two different sizes of the impurity species. Anomalous maximum is seen for a larger size of the impurity species in the case of the rigid host as compared to flexible host. The second anomalous diffusivity disappears with decrease in ih in flexible bcc solid. For one of the ih where double diffusivity maxima are observed, various properties are analysed to understand the anomalous diffusion behaviour. The impurity with anomalous diffusion has lower activation energy as compared to other impurities. Among the two anomalous impurities, the impurity with higher diffusivity has lower activation energy. The anomalous regime impurities as associated with velocity autocorrelation function with little or no backscattering, minimum average mean square force due to host atoms, lower activation energy. The self intermediate scattering function shows faster decay and a single relaxation time for anomalous regime impurity and two relaxation times for other impurity sizes. The wavenumber dependence of diffusivity of impurities shows oscillatory behaviour except for the anomalous regime impurities which show monotonic dependence on wavenumber. Chapter 7 discusses the influence of temperature induced solid-liquid phase transition on the size-dependent diffusivity. We report results for two distinct cases: (a) when the phase change is associated with corresponding changes in density and (b) when the phase change occurs at constant density. The latter is carried out so as to obtain the influence of disorder on the size-dependent diffusion or Levitation Effect. Studies with variable density are useful to understand the effect of disorder as well as change in density on size-dependent diffusivity. Two diffusivity maxima in the solid face-centred cubic phase is seen when the impurity-medium interaction is sufficiently large. One of these diffusivity maximum disappears with decrease in h. The impurities near the diffusivity maximum show velocity autocorrelation function with little backscattering, minimum in the average mean square force, lower activation energy, faster decay of self intermediate scattering function with a single relaxation time and a monotonic decay in wavevector dependence of diffusivity. Chapter 8 reports molecular dynamics simulations of a model guest tetrahedral molecule AX4 with differing bond lengths lAX have been carried out in a sphere with different surface roughness. The rotational-diffusion coefficient Dr shows a maximum for a particular value of lAX. This corresponds to the distance at which the interaction of the guest with the atoms of the host is most favourable. Although, the intensity of the maximum decreases with increase in the roughness of the confining surface, it is seen that the maximum exists even for a reasonably high degree of roughness. The observed maximum arises from the minimum in the torque on the tetrahedral molecule from its interaction with the confining medium due to mutual cancellation of forces. Activation energy for rotation is seen to be also a minimum for the bond length for which Dr is a maximum. These results suggest that there is a maximum in the rotational-diffusion coefficient when the rotating molecule is confined to a sphere of comparable size similar to the maximum in translational diffusion coefficient seen in porous solids and known as the Levitation Effect. On increase in the roughness of the sphere surface, the value of lAX at which the maximum in Dr is seen decreases. This is similar to the shift seen in the size of the diffusant corresponding to maximum diffusivity in the case of translational diffusivity. In Chapter 9 possible extensions to the work reported in the previous chapters and the directions to take are discussed. Symmetry plays an important role in size dependent diffusivity maximum in microporous crystalline solids; it would be interesting to investigate if similar role of symmetry exists in case of liquids and other disordered solids. Previous work from this laboratory on ions in water has shown the importance of electrostatic interactions. In the light of this, it would be interesting to see the influence of long-range interactions in breakdown of Stokes-Einstein relationship in liquids. Effect of density of the medium on impurity diffusion can be studied over a wide range of densities in case of supercritical fluids such as ions in water (where electrostatic interactions are present) and these can provide greater insight into dependence of diffusion on density. The origin of two diffusivity maxima in case of body-centered and face-centred cubic solids needs a detailed investigation to understand its origin. Quantification of disorder and its effect on size dependence of diffusion would be of interest. A detailed comparison with experimental data of matrix isolated molecules to understand and verify the dependence of rotational diffusivity on the size of the molecule as well as the cavity radius would be instructive.