The marriage of two very powerful techniques - cryogenic matrix isolation spectroscopy and seeded supersonic molecular beams - has led to the development of a novel type of cryogenic matrix isolation spectroscopy in ultracold, near 0 K, He droplets. The technique known as helium nanodroplet isolation (HENDI) has seen tremendeous experimental interest over the past 20 years; this in turn has resulted in the availability of spectroscopic data for many molecules and clusters embedded in He clusters. The experimental findings havemotivated a large number of theoretical calculations. This dissertation focuses on theoretical and computational studies of the rotational dynamics of weakly bound van der Waals clusters with its main theme being the dynamics of molecules and small molecular dimers embedded in superfluid He-4 nanodroplets. The single molecular dopant systems studied were clusters of HCN-(He)N, HX-(He)N, where X = F, Cl, Br as well as NH3-(He)N, with N = 1 - 20. Ground and excited state calculations were performed using the rigid body diffusion Monte Carlo (RBDMC) algorithm. For the excited state calculations a new approach was developed: adiabatic-node DMC (ANDMC). The ANDMC method was used to study the renormalization of molecular rotational constants in He droplets. It revealed that the dynamics depend on a delicate interplay between the gas phase rotational constant value and the anisotropies in the potential energy interaction between the He atom and the dopant. Also presented are the results of the first DMC simulations of the ammonia dimer doped into a small droplet of He-4. Further, a new approach to finding nodal surfaces for DMC simulations was developed that involved using a genetic algorithm (GA). This method was implemented to systematically and automatically compute nodal surfaces of excited states of the HCN-He complex and of the interchange tunneling splitting in the hydrogen-bonded HCl-HCl complex. The classical rotational dynamics of HX-He complexes with X = F, Cl, Br, CN were studied to gain insight into quantum simulations and revealed highly chaotic dynamics for states with J > 0. Fractal Weyl law behavior in an open, chaotic Hamiltonian system is the subject of the final chapter.

No description available.

High quality crystalline semiconductor films are a key component in the production of electronic and opto-electronic devices, however, the requirement of latticed-matched single crystal substrates for the epitaxy of a thin film limits the available material systems which can be developed commercially. This strict lattice matching requirement is relaxed for two-dimensional layered materials grown via van der Waals epitaxy. Unfortunately, the same low surface energies of these layered materials also suppress the growth of three-dimensional materials upon them, preventing direct large area single-crystal growth. The work presented in this thesis will demonstrate and investigate the spontaneous van der Waals epitaxy, driven by weak chemical interaction, of a three-dimensional material on a three-dimensional material system. Despite a 3.7% lattice mismatch, high quality CdTe can be heteroepitaxially deposited on α-Al2O3 but with an incommensurate interface which demonstrates weak adhesion between the film/substrate. This weak adhesion is exploited by developing a strain driven epitaxial thin film transfer and handling method, which causes deposited layers and structures to separate at the substrate interface for transfer to secondary carrier substrates without effecting the film properties and leaving the original substrate for subsequent use. Simple transferred thin film crystalline II-VI heterostructure devices on flexible substrates are demonstrated, without the need for selective chemical etch layers, ion-implantation or complex post-processes as required by conventional fabrication techniques. Following a growth study of GaAs on three oxide substrates, the phenomena of epitaxial registry with apparent weak interface adhesion is demonstrated for another system, GaAs/α-Al2O3, where a layer transferred heterostructure device on a flexible substrate is also demonstrated. / Thesis / Doctor of Philosophy (PhD)

Nonlinear frequency conversion provides essential tools for generating new colors and quantum states of light. Conventional nonlinear crystals have the problem of relative lower nonlinear susceptibilities, which result in the large footprint of devices and low efficient. Transition metal dichalcogenides possess huge nonlinear susceptibilities; further, 3R-stacked transition metal dichalcogenide crystals possess aligned layers with broken inversion symmetry, representing ideal candidates to boost the nonlinear optical gain with minimal footprint. Here we report the second-order nonlinear processes of 3R-MoS2 along the ordinary and extraordinary directions. Along the ordinary axis, by measuring the thickness-dependent second-harmonic generation, we present the first measurement of the second harmonic-generation coherence length of 3R-MoS2 and achieve record nonlinear optical enhancement from a van der Waals material, >104 stronger than a monolayer. It is found that 3R-MoS2 slabs exhibit similar conversion efficiencies of lithium niobate, but within 100-fold shorter propagation lengths. Furthermore, along the extraordinary axis, we achieve broadly tunable second-harmonic generation from 3R-MoS2 in a waveguide geometry, revealing the coherence length in such a structure. We characterize the full refractive-index spectrum and quantify its birefringence with near-field nanoimaging. In order to bring 3R-MoS2 into the application field, we have developed two fabrication methods: low-cost femtosecond laser etching and cleanroom nanolithography-based processes. The femtosecond laser writing setup offers a rapid, residue-free, and in-situ method for patterning grating structures. On the other hand, the cleanroom process can provide structures with higher resolution. The cleanroom fabrication process is based on SF6 RIE and E-beam lithography, which can narrow down the minimum linewidth to ~120nm. To achieve mode matching in waveguiding second-order nonlinear conversion, we utilized the mode dispersion relation calculated by an anisotropic model to find the overlapping of wavevectors among different photon energies. We proposed a molybdenum disulfide on silicon nitride structure (MOSS) to further unleash the potential of 3R-MoS2 in optical parametric conversion. Photonic structure optimization was performed using the Lumerical FDTD simulator, achieving a 90% coupling efficiency from SiN to 3R-MoS2 with a taper structure. With a taper length of 50μm, we successfully maintained a single mode of excitation wave in MoS2, which could provide a monotonoic mode source for nonlinear conversion. Our work highlights the potential of 3R-stacked transition metal dichalcogenides for integrated photonics, providing critical parameters, developing high-resolution fabrication processes, and offering initial designs for highly efficient on-chip nonlinear optical devices including periodically poled structures, optical parametric oscillators and amplifiers, and quantum circuits.

No description available.

Van der Waals-Wechselwirkungen (vdW) sind allgegenwärtig und spielen eine zentrale Rolle in einer großen Anzahl biologischer und moderner synthetischer Materialien. Die am weitesten verbreitete theoretische Methode zur Berechnung von Materialeigenschaften, die Dichtefunktionaltheorie (DFT) in semilokaler Näherung, vernachlässigt diese Wechselwirkungen jedoch größtenteils, was zur Entwicklung vieler verschiedener vdW-Modelle führte. Die hier vorgestellte Arbeit ebnet den Weg hin zu einem vereinheitlichten vdW-Modell welches die besten Elemente der unterschiedlichen Klassen von vdW-Modellen vereint. Zu diesem Zweck haben wir einen vereinheitlichten theoretischen Rahmen geschaffen, der auf dem Reichweite-separierten Adiabatischer-Zusammenhang-Fluktuations-Dissipations-Theorem aufbaut und die meisten existierenden vdW-Modelle umfasst. Wir analysieren die MBD-korrelierte Wellenfunktion am prototypischen Beispiel von π–π-Wechselwirkungen in supramolekularen Komplexen und stellen fest, dass diese Wechselwirkungen größtenteils durch delokalisierte kollektive Ladungsfluktuationen entstehen. Um zu dem langreichweitigen vdW-Modell ein ausgewogenes kurzreichweitiges Dichtefunktional zu identifizieren, präsentieren wir eine umfassende Untersuchung zum Zusammenspiel der kurz- und langreichweitigen Energiebeiträge in acht semilokalen Funktionalen und drei vdW-Modellen für eine große Spanne von Systemen. Die Bindungsenergieprofile vieler der DFT+vdW-Kombinationen unterscheiden sich sowohl quantitativ als auch qualitativ stark voneinander. Schließlich untersuchen wir die Performance des Vydrov–Van Voorhis-Polarisierbarkeitsfunktionals über das Periodensystem der Elemente hinweg und identifizieren eine systematische Unterschätzung der Polarisierbarkeiten und vdW-C₆-Koeffizienten für s- und d-Block-Elemente. Als Lösung entwickeln wir eine orbitalabhängige Verallgemeinerung des Funktionals. / The ubiquitous long-range van der Waals interactions play a central role in nearly all biological and modern synthetic materials. Yet the most widely used theoretical method for calculating material properties, the density functional theory (DFT) in semilocal approximation, largely neglects these interactions, which motivated the development of many different vdW models. The work in this thesis paves way towards a unified vdW model that combines best elements from the different classes of the vdW models. To this end, we developed a unified theoretical framework based on the range-separated adiabatic-connection fluctuation--dissipation theorem that encompasses most existing vdW models. We analyze the MBD correlated wave function on the prototypical case of π–π interactions in supramolecular complexes and find that these interactions are largely driven by delocalized collective charge fluctuations. To identify a balanced short-range density functional to accompany the long-range vdW model, we present a comprehensive study of the interplay between the short-range and long-range energy contributions in eight semilocal functionals and three vdW models on a wide range of systems. The binding-energy profiles of many of the DFT+vdW combinations differ both quantitatively and qualitatively, and some of the qualitative differences are independent of the choice of the vdW model. Finally, we investigate the performance of the Vydrov—Van Voorhis polarizability functional across the periodic table, identify systematic underestimation of the polarizabilities and vdW C₆ coefficients for s- and d-block elements, and develop an orbital-dependent generalization of this functional to resolve the issue.

The fast progress in the exploration of 2D materials such as graphene became possible due to development of fabrication techniques that allowed these materials to be protected from e.g. undesirable doping and gave rise to new functionalities realized within van der Waals heterostructures. Attracted by van der Waals interaction the constituent layers of such heterostructures preserve their exceptional electronic quality and for example in graphene allow for high electron mobility to be achieved. However, the studies of atomically thin layers such as NbSe2 that exhibit metallic behavior have been impeded by their reactivity and hence oxidation during exposure to ambient or oxidizing agents such as solvents. In this thesis, the existing heterostructure assembly technique was improved by the introduction of exfoliation and re-stacking by a fully motorized system placed in an inert atmosphere. This approach allowed us to overcome the problem of environmental degradation and create Hall bars and planar tunnel junctions from atomically thin superconducting NbSe2. Furthermore, this versatile approach allowed us to study the thickness dependence of the normal and superconducting state transport properties of NbSe2, uncovering the reduction of the superconducting energy gap and transition temperature in the thinnest samples. On the other hand, 2D materials being just 1-3 atoms thick represent an ultimate example of a membrane - thin but laterally extended object. Consisting of such atomically thin membranes the van der Waals heterostructures can be used for purposes other than the studies of electronic transport. In this work, ubiquitous bubbles occurring during van der Waals heterostructure assembly are employed as a tool to explore 2D materials' mechanical properties and mutual adhesion. This allowed us to measure Young's modulus of graphene and other 2D materials under 1-2% strain and deduce the internal pressure that can reach up to 1 GPa in sub-nanometer size bubbles.

Made available in DSpace on 2014-06-11T19:30:18Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-03-15Bitstream added on 2014-06-13T21:00:47Z : No. of bitstreams: 1 nova_cv_me_bauru.pdf: 1980542 bytes, checksum: 9aad1da39bf5c30c6e4d38ca0be07fef (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / A teoria cinética dos gases tem como primeira aproximação o comportamento observado considerando o gás como tendo um comportamento ideal, isto é, pode ser modelado através da lei do gás ideal. As equações de estado conhecidas, como a equação do gás ideal e de van der Waals descrevem, dentro das aproximações do modelo, situações bastante diversas. Neste trabalho iremos utilizar a lei dos gases ideais, ou mais especificamente a implementação da Equação de van der Waals para o entendimento do fenômeno de colisões que entre átomos e moléculas / The kinetic theory of gases has a a first approximation the observed behavior considering the gas to have an ideal behavior, ie it can be modeled by the ideal bas law. The equations of state known as the ideal gas equation and Van der Waals describe, within the approximations of the model, very different situations. In this paper we use the ideal gas law, or more specifically the implementation of the Vann der Waals equation for understandign the phenomenon of collisions between atoms and molecules

Orientador: Adalberto Bono Maurizio Sacci Bassi / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-17T03:59:51Z (GMT). No. of bitstreams: 1 Guerrero_AndredeOliveira_M.pdf: 4353295 bytes, checksum: a8e573ea1fa805457349a7a1d9c37925 (MD5) Previous issue date: 2010 / Resumo: A equação original de van der Waals é alterada de modo a aprimorar sua aderência a dados experimentais para o Argônio, desde as baixas densidades dos estados gasosos até as altas densidades dos líquidos e dos vidros. Isto permite a obtenção de uma curva spinodal (fronteira termodinâmica entre os estados não acessíveis pela matéria e os estados possíveis, estáveis ou não) mais precisa do que a atualmente disponível, além de fornecer subsídios para estudos de líquidos e gases não estáveis. A pressão repulsiva original é substituída pela pressão de um sistema de esferas rígidas, enquanto que a pressão atrativa original é substituída pela pressão de um campo médio isotrópico descrito por três parâmetros. A realização destas alterações propicia a discussão de diversos aspectos da interpretação física da equação de van der Waals. Como os estados considerados são homogêneos, mas não necessariamente estados de equilíbrio, a temporal termodinâmica dos meios homogêneos é uma teoria adequada à descrição dos estados representados pela equação alterada. / Abstract: The original van der Waals equation is altered to improve its quantitative description of argon experimental values, including those of low density gaseous states and high density liquids and glasses. A spinodal curve is obtained (the limit between thermodynamically forbidden and permitted states of matter, either stable or unstable) that is more precise than the one actually available and reveals more information for studying unstable gases and liquids. The pressure of a rigid spheres system substitutes the original repulsive pressure, while the pressure of an isotropic mean field defined by three parameters substitutes the original attractive pressure. Implementing these substitutions provokes the discussion of several aspects, related to the physical meaning of van der Waals equation. Since only homogeneous states are considered, although they are not necessarily equilibrium states, time dependent thermodynamics of homogeneous media is an adequate theory to describe the states represented by the altered equation. / Mestrado / Físico-Química / Mestre em Química

Orientador: Adalberto Bono Maurizio Sacchi Bassi / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-20T13:03:52Z (GMT). No. of bitstreams: 1 Florindo_CaioCesarFerreira_M.pdf: 1544899 bytes, checksum: 0eba46471eda7b3f002b978841cb2411 (MD5) Previous issue date: 2012 / Resumo: O presente trabalho tem três metas principais: (1) usar as transformações de Levin para estimar coeficientes viriais e avaliar a qualidade das estimativas; (2) inserir adaptações, coerentes com as transformações de Levin, na equação original de van der Waals, de modo a aprimorar sua capacidade de se aproximar de dados experimentais para estados estáveis; (3) extrapolar a equação adaptada, para possibilitar o estudo de estados não estáveis. Os resultados indicam que as transformações de Levin podem ser usadas como uma forma aproximada de representar a série virial, porque os coeficientes viriais de alta ordem, por elas estimados, estão em boa concordância com os valores obtidos na literatura. A utilização das representações de Levin para a adaptação do termo repulsivo da equação de van der Waals, juntamente com uma alteração proposta para o termo atrativo, produz isotermas subcríticas e supercríticas em boa concordância com os dados experimentais e proporciona aprimoramento da previsão do comportamento do sistema. As novas equações podem ser aplicadas tanto em densidades referentes à região de fase gasosa, como de fase líquida. Devido às boas previsões de resultados produzidas pelas equações desenvolvidas neste trabalho, são obtidas curvas spinodais com um nível de exatidão muito superior àquele encontrado na literatura. Portanto, o presente trabalho descreve equações aprimoradas que representam estados estáveis tão bem que podem ser extrapoladas para estados não estáveis / Abstract: This work aims at three main goals: (1) to use Levin's sequence transformations for estimating virial coefficients, and to assess the quality of the estimates; (2) to insert in the van der Waals equation some modifications consistent with the Levin's sequence transformations, enhancing its ability to approximate experimental data for stable states; (3) to extrapolate the modified equation for studying unstable states. The results indicate that the Levin's sequence transformations can be used as an approximate way to represent the virial series, because the high order estimated virial coefficients are in good agreement with values reported in literature. The use of the Levin's sequence transformations for modifying the repulsive term of van der Waals equation, together with a proposed attractive term improvement, yields subcritical and supercritical isotherms in good agreement with experimental data and provides better predictions of the behavior of the system. The new equations can be applied both at densities corresponding to gaseous and liquid phases. According to the good predictions of experimental results produced by the equations developed in this work, spinodal curves which are much more accurate than those found in literature are obtained. Therefore, this work describes improved equations that represent stable states well enough to accept extrapolation to unstable states / Mestrado / Físico-Química / Mestre em Química