Rozprawy doktorskie na temat „Discrete Electronic Energy States”

Kyoto University (京都大学)
0048
新制・課程博士
博士(工学)
甲第14161号
工博第2995号
新制||工||1444(附属図書館)
26467
UT51-2008-N478
京都大学大学院工学研究科マイクロエンジニアリング専攻
(主査)教授 立花 明知, 教授 榊 茂好, 教授 木村 健二
学位規則第4条第1項該当

This thesis is concerned with theoretical calculations of the properties of electronic bound states in semiconductor heterostructures. The complex band structure empirical pseudopotential method (EPM) is used as the foundation of the work. Spin orbit coupling and strain effects (due to lattice mismatch) are included in familiar ways, as is the transfer matrix method, allowing the study of arbitrarily configured heterostructures. These techniques are used to investigate the unusually deep InAs/AlSb conduction band well. The strong possibility of intraband transitions at electro magnetic wavelengths around 1.55µm is predicted, with corresponding enhanced momentum matrix elements and joint density of states over interband transitions. An InAs/GaSb/AlSb asymmetric well is investigated, paying particular attention to the bound states in the vicinity of the InAs/GaSb band overlap. The electron-like states are found to cross with heavy hole and anti-cross with light hole-like states, as a function of heterostructure dimension or applied electrostatic field. This is analogous to the hybridisation of states in the in-plane band structure, except that for zero in-plane wave vector there can be no appreciable hybridisation of electron and heavy hole states. A technique is described that has been developed to extract envelope functions from heterostructure wavefunctions calculated using the realistic complex band structure EPM approach. These envelope functions conform to Burt’s theory (M. G. Burt, J. Phys.: Condens. Matt. 4, 6651 (1992)) in that they are uniquely defined, continuous and smooth over all space. Comparisons with traditional effective mass envelope functions are made. The extracted envelope functions are used to demonstrate conclusively Burt's predictions (M. G. Burt, Superlatt. Mi- crostruct. 17, 335 (1995)) concerning the inadequacy of certain approximations for the calculation of interband dipole matrix elements and charge oscillation. Finally, the issue of k • p operator ordering is convincingly settled, in favour of 'ordered' over 'symmetrised' Hamiltonians, by comparison to EPM calculations, and using EPM derived k • p parameters.

We study the unique phenomena which occur in certain systems characterized by the crossing or avoided crossing of two electronic eigenvalues. First, an example problem will be investigated for a given Hamiltonian resulting in a codimension 1 crossing by implementing results by Hagedorn from 1994. Then we perturb the Hamiltonian to study the system for the corresponding avoided crossing by implementing results by Hagedorn and Joye from 1998. The results from these demonstrate the behavior which occurs at a codimension 1 crossing and avoided crossing and illustrates the differences. These solutions may also be used in further studies with Herman-Kluk propagation and more. Secondly, we study codimension 2 crossings by considering a more general type of wave packet. We focus on the case of Schrödinger equation but our methods are general enough to be adapted to other systems with the geometric conditions therein. The motivation comes from the construction of surface hopping algorithms giving an approximation of the solution of a system of Schrödinger equations coupled by a potential admitting a conical intersection, in the spirit of Herman-Kluk approximation (in close relation with frozen/thawed approximations). Our main Theorem gives explicit transition formulas for the profiles when passing through a conical crossing point, including precise computation of the transformation of the phase and its proof is based on a normal form approach.
Doctor of Philosophy
We study energies of molecular systems in which special circumstances occur. In particular, when these energies intersect, or come close to intersecting. These phenomena give rise to unique physics which allows special reactions to occur and are thus of interest to study. We study one example of a more specific type of energy level crossing and avoided crossing, and then consider another type of crossing in a more general setting. We find solutions for these systems to draw our results from.

Group 3 metal clusters are synthesized by laser vaporization in a pulsed cluster beam source and identified with laser ionization time-of-flight mass spectrometry. The adiabatic ionization energies and vibrational frequencies of these clusters are measured using mass-analyzed threshold ionization (MATI) spectroscopy. Their structures and electronic states are determined by combining the MATI spectra with quantum chemical calculations and spectral simulations. This dissertation focuses on the study of several small molecules, which include LaO2, La2, M2O2, M3O4, M3C2, and La3C2O, where M = Sc, Y, and La. Except for La2, these molecules exhibit strong ionic characters between the metal and oxygen or carbon atoms and can be described as [O-][La2+][O-], [M2+]2[O2-]2, [M8/3+]3[O2-]4, [M2+]3[C3-]2, and [La8/3+]3[C3-]2[O2-]. The interactions between the metal atoms form covalent bonds, which can be described by a triple bond in La2, a two-center two electron bond in M2O2, a three-center one electron bond in M3O4, and a three-center three electron bond in M3C2. In addition, the electron in the non-bonding highest occupied molecular orbital (HOMO) is localized in the La 6s orbital in LaO2 and La3C2O. The ground states of these molecules are all in low electron-spin states with the spin multiplicities of 1 or 2. Although the ground electronic state of LaO2 is a linear structure, the excited quartet state of the molecule is determined to be a bent structure. M2O2 and M3O4 have the planar rhombic and cage-like structures, respectively; whereas M3C2 has a trigonal bipyramid structure. La3C2O is formed by oxygen binding with two La atoms of La3C2. Ionization removes a metal-based (n+1)s electron in all neutral molecules, and the resultant ions have similar geometries to those of the corresponding neutral states. In the case of La2, additional ionization of a La 5d electron is also observed.

The vibrational potential energy surfaces in electronic ground and excited states of several ring molecules were investigated using several different spectroscopic methods, including far-infrared (IR), Raman, ultraviolet (UV) absorption, fluorescence excitation (FES), and single vibronic level fluorescence (SVLF) spectroscopies. Based on new information obtained from SVLF and millimeter wave spectra, the far-IR spectra of coumaran were reassigned and the one-dimensional ring-puckering potential energy functions for several vibrational states in the S0 ground state were determined. The barrier was found to be 154 cm-1 and the puckering angles to be ± 25°, in good agreement with the millimeter wave barrier of 152 cm-1 and puckering angles of ± 23°. Moreover, the UV absorption and FES spectra of coumaran allowed the one-dimensional ring-puckering potential energy functions in the S1 excited state to be determined. The puckering barrier is 34 cm-1 for the excited state and the puckering angles are ± 14°. Several calculations with different basis sets have been carried out to better understand the unusual vibrational frequencies of cyclopropenone. It was shown that there is strong interaction between the C=O and symmetric C-C stretching vibrations. These results differ quantitatively from a previous normal coordinate calculation and interpretation. The vapor-phase Raman spectrum of 3,7-dioxabicyclo[3.3.0]oct-1,5-ene was analyzed and compared to the predicted spectrum from DFT calculations. The spectrum further shows it has D2h symmetry, in which the skeletons of both rings are planar. The infrared and Raman spectra of vapor-phase and liquid-phase 1,4-benzodioxan and 1,2,3,4-tetrahydronaphthalene were collected and the complete vibrational assignments for both molecules were made. Theoretical calculations predicted the barriers to planarity to be 4809 cm-1 for 1,2,3,4-tetrahydonaphthalene and 4095 cm-1 for 1,4-benzodioxan. The UV absorption, FES, and SVLF spectra of both molecules were recorded and assigned. Both one and two-dimensional potential energy functions of 1,4-benzodioxan for the ring-twisting and ring-bending vibrations were carried out for the S0 and S1(π,π*) states, and these were consistent with the high barriers calculated for both states. The low-frequency spectra of 1,2,3,4-tetrahydronaphthalene in both S0 and S1(π,π*) states were also analyzed.

Physics
Ph.D.
The quantum interference effects, such as the Autler-Townes (AT) effect and electromagnetically induced transparency (EIT) applied to molecular systems are the focus of this Dissertation in the context of high resolution molecular spectroscopy. We demonstrate that the AT effect can be used to manipulate the spin character of a spin-orbit coupled pair of molecular energy levels serving as a \textit{gateway} between the singlet and triplet electronic states. We demonstrate that the singlet-triplet mixing characters of the \textit{gateway} levels can be controlled by manipulating the coupling laser \textit{E} field amplitude. We observe experimentally the collisional population transfer between electronic states $G^1\Pi_g (v=12, J=21, f)$ and $1^3\Sigma _g^-(v=1, N=21, f)$ of $^7$Li$_2$. We obtain the Stern-Vollmer plot according to the vapor pressure dependence of collisional transfer rate. The triplet fluorescence from the mixed \textit{gateway} levels to the triplet $b^3\Pi_u(v'=1,J'=
Temple University--Theses

The electronical and structural properties of TlSe-type chain-like crystals are the main topic of this study. A computational method which is Tight Binding method is introduced and used to obtain the electronic band structure of TlSe and TlInSe2 . For both materials the partial and total density of states are calculated. The results are compared with the other theoretical results.

Über die besonders hohe Effizienz von Halid-Perowskit (HaP)-basierten optoelektronischen Bauteilen wurde bereits in der Literatur berichtet. Um die Entwicklung dieser Bauteile voranzutreiben, ist ein umfassendes und verlässliches Verständnis derer elektronischen Struktur, sowie der Energielevelanordnung (ELA) an HaP Grenzflächen von größter Bedeutung. Demzufolge beschäftigt sich die vorliegende Arbeit mit der Untersuchung i) der Bandstruktur von Perowskit-Einkristallen, um ein solides Fundament für die Darlegung der elektronischen Eigenschaften von polykristallinen Dünnschichten zu erarbeiten, und mit ii) den Einflüssen von Oberflächenzuständen auf die elektronische Struktur der Oberfläche, sowie deren Rolle bei der Kontrolle von ELA an HaP Grenzflächen. Die Charakterisierung erfolgt überwiegend mithilfe von Photoelektronenspektroskopie (PES) und ergänzenden Messmethoden wie Beugung niederenergetischer Elektronen an Oberflächen, UV-VIS-Spektroskopie, Rasterkraftmikroskopie und Kelvin-Sonde. Erstens weist die Banddispersion von zwei prototypischen Perowskit-Einkristallen eine starke Dispersion des jeweiligen oberen Valenzbandes (VB) auf, dessen globales Maximum in beiden Fällen am R-Punkt in der Brillouin-Zone liegt. Dabei wird eine effektive Lochmasse von 0.25 m0 für CH3NH3PbBr3, bzw. von ~0.50 m0 für CH3NH3PbI3 bestimmt. Basierend auf diesen Ergebnissen werden die elektronischen Spektren von polykristallinen Dünnschichten konstruiert und es wird dadurch aufgezeigt, dass eine Bestimmung der Valenzbandkantenposition ausgehend von einer logarithmischen Intensitätsskala aufgrund von geringer Zustandsdichte am VB Maximum vorzuziehen ist. Zweitens stellt sich bei der Untersuchung der elektronischen Struktur von frisch präparierten Perowskit-Oberflächen heraus, dass die n-Typ Eigenschaft eine Folge der Bandverbiegung ist, welche durch donatorartige Oberflächenzustände hervorgerufen wird. Des Weiteren weisen die PES-Messungen an Perowskiten mit unterschiedlichen Zusammensetzungen aufgrund von Oberflächenphotospannung eine Anregungslichtintensitätsabhängigkeit der Energieniveaus von bis zu 0.7 eV auf. Darüber hinaus wird die Kontrolle von ELA durch gezielte Variation der Oberflächenzustandsdichte gezeigt, wodurch sich unterschiedliche ELA-Lagen (mit Abweichungen von über 0.5 eV) an den Grenzflächen mit organischen Akzeptormolekülen erklären lassen. Die vorliegenden Ergebnisse verhelfen dazu, die starke Abweichung der in der Literatur berichteten Energieniveaus zu erklären und somit ein verfeinertes Verständnis des Funktionsprinzips von perowskit-basierten Bauteilen zu erlangen.
Optoelectronic devices based on halide perovskites (HaPs) and possessing remarkably high performance have been reported. To push the development of such devices even further, a comprehensive and reliable understanding of their electronic structure, including the energy level alignment (ELA) at HaPs interfaces, is essential but presently not available. In an attempt to get a deep insight into the electronic properties of HaPs and the related interfaces, the work presented in this thesis investigates i) the fundamental band structure of perovskite single crystals, in order to establish solid foundations for a better understanding the electronic properties of polycrystalline thin films and ii) the effects of surface states on the surface electronic structure and their role in controlling the ELA at HaPs interfaces. The characterization is mostly performed using photoelectron spectroscopy, together with complementary techniques including low-energy electron diffraction, UV-vis absorption spectroscopy, atomic force microscopy and Kelvin probe measurements. Firstly, the band structure of two prototypical perovskite single crystals is unraveled, featuring widely dispersing top valence bands (VB) with the global valence band maximum at R point of the Brillouin zone. The hole effective masses there are determined to be ~0.25 m0 for CH3NH3PbBr3 and ~0.50 m0 for CH3NH3PbI3. Based on these results, the energy distribution curves of polycrystalline thin films are constructed, revealing the fact that using a logarithmic intensity scale to determine the VB onset is preferable due to the low density of states at the VB maximum. Secondly, investigations on the surface electronic structure of pristine perovskite surfaces conclude that the n-type behavior is a result of surface band bending due to the presence of donor-type surface states. Furthermore, due to surface photovoltage effect, photoemission measurements on different perovskite compositions exhibit excitation-intensity dependent energy levels with a shift of up to 0.7 eV. Eventually, control over the ELA by manipulating the density of surface states is demonstrated, from which very different ELA situations (variation over 0.5 eV) at interfaces with organic electron acceptor molecules are rationalized. Our findings further help to explain the rather dissimilar reported energy levels at perovskite surfaces and interfaces, refining our understanding of the operational principles in perovskite related devices.

In dieser Dissertation werden ab initio Theorien zur Beschreibung der Zustände von perfekten halbleitenden und nichtleitenden Kristallen, unter Berücksichtigung elektronischer Korrelationen, abgeleitet und angewandt. Als Ausgangsbasis dient hierzu die Hartree-Fock Approximation in Verbindung mit Wannier-Orbitalen. Darauf aufbauend studiere ich zunächst in Teil I der Abhandlung den Grundzustand der wasserstoffbrückengebundenen Fluorwasserstoff und Chlorwasserstoff zick-zack Ketten und analysiere die langreichweitigen Korrelationsbeiträge. Dabei mache ich die Basissatzextrapolationstechniken, die für kleine Moleküle entwickelt wurden, zur Berechnung von hochgenauen Bindungsenergien von Kristallen nutzbar. In Teil II der Arbeit leite ich zunächst eine quantenfeldtheoretische ab initio Beschreibung von Elektroneneinfangzuständen und Lochzuständen in Kristallen her. Grundlage hierbei ist das etablierte algebraische diagrammatische Konstruktionsschema (ADC) zur Approximation der Selbstenergie für die Bestimmung der Vielteilchen-Green's-Funktion mittels der Dyson-Gleichung. Die volle Translationssymmetrie des Problems wird hierbei beachtet und die Lokalität elektronischer Korrelationen ausgenutzt. Das resultierende Schema wird Kristallorbital-ADC (CO-ADC) genannt. Ich berechne damit die Quasiteilchenbandstruktur einer Fluorwasserstoffkette und eines Lithiumfluoridkristalls. In beiden Fällen erhalte ich eine sehr gute Übereinstimmung zwischen meinen Resultaten und den Ergebnissen aus anderen Methoden
In this dissertation, theories for the ab initio description of the states of perfect semiconducting and insulating crystals are derived and applied. Electron correlations are treated thoroughly based on the Hartree-Fock approximation formulated in terms of Wannier orbitals. In part I of the treatise, I study the ground state of hydrogen-bonded hydrogen fluoride and hydrogen chloride zig-zag chains. I analyse the long-range contributions of electron correlations. Thereby, I employ basis set extrapolation techniques, which have originally been developed for small molecules, to also obtain highly accurate binding energies of crystals. In part II of the thesis, I devise an ab initio description of the electron attachment and electron removal states of crystals using methods of quantum field theory. I harness the well-established algebraic diagrammatic construction scheme (ADC) to approximate the self-energy, used in conjunction with the Dyson equation, to determine the many-particle Green's function for crystals. Thereby, the translational symmetry of the problem and the locality of electron correlations are fully exploited. The resulting scheme is termed crystal orbital ADC (CO-ADC). It is applied to obtain the quasiparticle band structure of a hydrogen fluoride chain and a lithium fluoride crystal. In both cases, a very good agreement of my results to those determined with other methods is observed

This thesis is devoted to the optical properties of low-dimensional structures based on such two-dimensional materials as graphene, silicene and phosphorene. We investigate optical properties of a variety of quasi-one dimensional and quasi-zero-dimensional structures, which are promising for future optoelectronics. Primarily we focus on their low-energy optical properties and how these properties are influenced by the structures’ geometry, external fields, intrinsic strain and edge disorder. As a consequence of this endeavor, we find several interesting effects such as correlation between the optical properties of tubes and ribbons whose periodic and ‘hard wall’ boundary conditions are matched and a universal value of matrix element in narrow-gap tubes and ribbons characterizing probability of transitions across the band gap opened up by intrinsic strain originating from the tube’s surface curvature or ribbon’s edge relaxation. The analytical study of the gapped 2D Dirac materials such as silicene and germanene, which have some similarity to the aforementioned quasi-one-dimensional systems in terms of physical description, reveals a valley- and polarization-dependent selection rules. It was also found that absorption coefficient should change in gapped materials with increasing frequency and become a half of its value for gap edge transitions when the spectrum is linear. Our analysis of the electronic properties of flat clusters of silicene and phosphorene relates the emergence and the number of the peculiar edge states localized at zero energy, so-called zero-energy states, which are know to be of topological origin, to the cluster’s structural characteristics such as shape and size. This allows to predict the presence and the number of such states avoiding complicated topological arguments and provides a recipes for design of metallic and dielectric clusters. We show that zero-energy states are optically active and can be efficiently manipulated by external electric field. However, the edge disorder is important to take into account. We present a new fractal-based methodology to study the effects of the edge disorder which can be applied also to modeling of composite materials. These finding should be useful in design of optoelectronic devices such as tunable emitters and detectors in a wide region of electromagnetic spectrum ranging form the mid-infrared and THz to the optical frequencies.

Les phases MAX sont des carbures et nitrures ternaires dont les propriétés sont intermédiaires entre celles de métaux et de céramiques. Ce travail de thèse a pour objectif de mesurer leur constante diélectrique complexe en fonction de la composition et de l'orientation cristallographique. Les échantillons utilisés sont des monocristaux élaborés en couches minces et des polycristaux massifs. Les mesures ont été effectuées par spectroscopie de perte d'énergie des électrons (EELS) et par l'ellipsométrie V-UV. Les propriétés diélectriques très différentes en fonction de l'orientation du cristal ont été mises en évidence et ont donc confirmé l'anisotropie suggérée par la théorie. L'étude d'autres composés en couches minces tel que Ti2GeC, Ti2SnC dont la synthèse a été réalisée nous a permis d'étudier l'influence des éléments A sur les propriétés diélectriques et optiques de ces matériaux. Un modèle phénoménologique semi-classique de Drude-Lorentz a été utilisé pour reproduire la fonction Ɛ. Après ajustement de ce modèle aux mesures expérimentales, il a été possible d'extraire la densité electronique et d'estimer un temps de relaxation des électrons libres. Les résultats sont en bon accord avec les valeurs publiées et nous permettent de confirmer que la conductivité statique présente une forte anisotropie dans Ti2A1C et Ti2A1N. Enfin, une approche ab initio a été mise en œuvre afin de modéliser les constantes diélectriques complexes. Ces calculs basés sur la théorie de la fonctionnelle de la densité dépendant du temps (TDDFT) reproduisent l'anisotropie de la réponse diélectrique et montrent qu'elle est intimement liée aux champs locaux
The MAX phases are ternary carbides and nitrides which exhibit remarkable properties half way between metals end ceramics. In this work, we have measured the complex dielectric constant Ɛ(ω) as a function of the composition of the sample. The samples are thin films of single crystal grown by magnetron sputtering and bulk polycristals processed by hot isostatic pressure. The measurements have been performed by electron energy loss spectroscopy (EELS) in the infrated - soft x-ray range and by V-UV ellipsometry in the infrated-ultraviolet range (1. 6 to 5. 5 eV). The dielctric properties of the Ti2A1C and Ti2A1N samples are remarkably different with the crystallographic orientation. In particular, a shift of the energy position of the plasmon of Ti1A1C with respect to the orientation of the crystal is observed. The dielectric constants of thin films of Ti2GeC, Ti2SnC and V2GeC have also been determined. A empirical semi-classical Drude-Lorentz model is fitted to the experimental spectra enabled us to extract the microscopic parameters such as the relaxation times and the electron density and the lifetime of free electrons. In addition, we show that the DC conductivity is indeed anisotropic in these compounds, a fact which has not been possible to address so far on macroscopic measurements. The dielectric function has been modelled in the framework of the time dependant density functional theory. Our calculations showed that the various dielctric functions in Ti2A1C are clearly influenced by strong local effect created by the presence of the d band in this material

Ce travail de these est consacre a l'elaboration et l'etude des proprietes electroniques de la phase quasicristalline alpdre. La recherche d'une procedure d'elaboration nous a permis d'obtenir des echantillons de phase icosaedrique pure de tres grande qualite structurale. L'alliage quasicristallin alpdre presente des proprietes de transport exceptionnelles pour un alliage constitue uniquement de metaux. En particulier, nous avons confirme que la valeur de resistivite de certains echantillons de i-alpdre peut atteindre #4#37 1 cm, ce qui est 10#6 fois superieure a celle des metaux standards, et 10#3 fois superieure a celles des amorphes metalliques. Les valeurs de resistivite de ces echantillons et leur dependance en temperature semblent s'approcher de celles des systemes ayant franchi la transition metal-isolant. Toutefois, il existe de fortes variations des proprietes de transport entre differents echantillons de la phase i-alpdre. D'autres echantillons ont montre des proprietes electroniques semblables a celles des phases icosaedriques bien connues i-alpdmn et i-alcufe qui se trouvent du cote metallique d'une transition metal-isolant. Nous avons etabli que ces disparites de proprietes de transport sont liees a des variations de composition et de qualite structurale. A l'inverse des metaux, meilleure est la qualite structurale plus la resistivite des echantillons est elevee ce qui exclu la possibilite d'une transition metal-isolant par le desordre (anderson) dans cette phase. D'autre part, nos mesures de densite d'etats electroniques permettent d'etablir la presence d'un pseudogap au niveau de fermi mais pas de gap reel comme dans les semi-conducteurs. On a donc affaire a un type de transport nouveau qui n'obeit pas aux lois connues dans les materiaux classiques (amorphes, semi-conducteurs, metaux). Un modele de transport par sauts entre etats critiques pourrait expliquer une transition metal-isolant dans ces structures ordonnees sans gap. Nous avons entrepris, par ailleurs, des mesures d'energie de surface de couches minces quasicristallines en collaboration avec l'industrie de revetements aps. Ces mesures, nous ont permis d'etablir que les couches minces quasicristallines ont une faible mouillabilite

Modèle de calcul de l'énergie électronique des alliages à base de métaux de transition. Ce modèle est base sur un hamiltonien de liaisons fortes et prend en compte les effets d'hybridation s-d. Calcul de la densité d'états électroniques et des énergies de cohésion. Pour les alliages amorphes de deux métaux de transition, un ordre chimique local est établi. Conséquences sur la densité d'états électronique. Corrélation entre structure électronique et coefficient de hall. Mise en évidence d'une forte hybridation sp-d pour les alliages entre métaux de transition et métaux polyvalents

Le centre d#-, ou ion donneur negatif, est l'analogue en physique du solide de l'ion hydrogene negatif h#-. Il s'agit donc d'un systeme correle simple, avec seulement deux electrons. Les transitions magneto-optiques permettant l'etude des donneurs peu profonds (neutres ou charges negativement) dans les multi-puits gaas/algaas se situent dans la gamme de l'infra-rouge lointain. Notre appareillage experimental est essentiellement constitue d'un spectrometre a transformee de fourier, couple a un aimant supraconducteur ou resistif. Nous avons etudie le mecanisme de formation des centres d#- confines dans des multi-puits quantiques. Dans cette configuration, contrairement au materiau massif, les centres d#- sont formes par construction, ce qui permet leur etude a l'equilibre thermodynamique. L'importance de la geometrie de dopage est soulignee, et la possibilite de realiser un dopage d#- de puits quantiques est mise en evidence. Le spectre d'energie des centres d#- confines a ete etudie pour une large gamme de champs magnetiques (jusqu'a 20 t) et pour differentes largeurs de puits. Ces mesures permettent d'observer, outre la non-parabolicite de bande de gaas, les effets de correlation electronique augmentes par la baisse de dimensionalite. L'etude des centres d#- en presence de desordre d'alliage dans des puits de al-gaas met en evidence la possibilite de coexistence, dans ce type de systeme, de centres profonds et de centres peu profonds, tous deux charges negativement

This thesis is organized as follows: Part I concerns with the theoretical background, Part II refers to publications, Finally, the main achievements are summarized and further possible applications are outlined in Part III.
Tese de doutoramento em Química (Pré-Bolonha), Especialidade de Química Teórica, apresentada à Faculdade de Ciências e Tecnologia da Universidade de Coimbra
Theoretical study on the N2 O molecular system is presented in this Ph.D. thesis: starting from the construction of a global potential energy surface for its ground electronic state, to dynamical studies of collisions taking place on it. The double many-body expansion (DMBE) method is employed in the construction of such potential function. The increasing interest in this system led us to also study the first singlet excited state of nitrous oxide, which would be also required for studying fully the dynamics and kinetics of N(2 D) + NO(X 2 Π) reaction. Exploratory trajectories have also been run on this DMBE form with the quasiclassical trajectory method, with the thermal rate constant so determined at room temperature significantly enhancing agreement with the experimental data.
Na presente tese é apresentado um estudo teórico sobre o sistema molecular N_2O: partindo da construção de uma superfície de energia potencial (SEP) global para o seu estado eletrónico fundamental até ao estudo da dinâmica das colisões que ocorrem neste sistema. O método de dupla expansão multicorpos (DMBE) é empregue na construção da função potencial. A topologia da nova superfície é caracterizada em detalhe. Uma comparação entre as propriedades dos pontos estacionários aqui obtidos com os relatados na literatura é apresentada, sendo as novas estruturas encontradas também caracterizados. A reacção de relevância atmosférica N2D + NO é estudada usando o método trajetórias quase-clássicas na nova SEP DMBE para o estado fundamental de N_2O. Comparações detalhadas com previsões teóricas e experimentais anteriores foram realizados. Os resultados obtidos apresentam maior reactividade do que outros métodos teóricos disponíveis na literatura. Um melhor acordo com os resultados experimentais é por conseguinte obtido, apesar the existem grandes incertezas experimentais. O crescente interesse neste sistema levou também ao estudo do primeiro estado singleto excitado do óxido nitroso, o qual é necessário para tratar de forma completa a dinâmica e cinética da reacção N(2D) + NO. Foram realizados nesta superfície DMBE estudos exploratórios usando o método das trajetórias quase-clássicas, tendo melhorado significativamente a concordância dos dados experimentais com a constante de velocidade termalizada obtida à temperatura ambiente.

Volatile anaesthetics are widely used in clinical practice to induct and maintain anaesthesia through inhalation. The major atmospheric effects that may arise from emission of volatile anaesthetics are their contributions to ozone depletion in the stratosphere and to greenhouse global warming. In this thesis we present spectroscopic studies on UVradiation and electron interaction with three of the volatile anaesthetics currently in use, sevoflurane (C4H3F7O), isoflurane (C3H2ClF5O) and halothane (C2HBrClF3), in order to comprehensively describe the underlying molecular mechanisms of these molecules yielding dissociation. Electron scattering elastic differential cross sections (DCS) by the three mentioned molecules were measured for energies from 8.0 eV to 50 eV. The experimental DCSs and integral cross sections (ICSs) were compared with theoretical calculations, performed by collaborating groups, using two different methodologies, the Schwinger multichannel method (SMC) and the independent atom model–screening corrected additivity rule (IAM-SCAR). Moreover, we present, for the same compounds, results from VUV photoabsorption measurements over the wavelength range 115-220 nm, together with ab initio theoretical calculations of the vertical excitation energies and oscillator strength. This combined experimental and theoretical study allows a comprehensive description and characterization of the electronic states of these chemical compounds. The measured photoabsorption cross sections were also used to calculate the photolysis lifetime of the molecules in the Earth’s atmosphere from ground level up to the limit of the stratopause.

In this work, experimental and theoretical approaches are applied to the study of chemical reaction dynamics. In Chapter 2, two applications of transition state theory are presented: (1) Application of microcanonical transition state theory to determine the rate constant of dissociation of C2F3I after π∗ ← π excitation. It was found that this reaction has a very fast rate constant and thus is a promising system for testing the statistical assumption of molecular reaction dynamics. (2) A general rate constant expression for the reaction of atoms and molecules at surfaces was derived within the statistical framework of flexible transition state theory. In Chapter 4, a computationally efficient TDDFT approach was found to produce useful potential energy surface landscapes for application to non-adiabatic predissociative dynamics of the molecule CS2 after excitation from the ground state to the singlet C-state. In Chapter 5, ultrafast experimental results of excitation of CS2 to the predissociative neutral singlet C-state is presented. The bandwidth of the excitation laser was carefully tuned to span a two-component scattering resonance with each component differently evolving electronically with respect to excited state character during the quasi-bound oscillation. Scalar time-resolved photoelectron spectra (TRPES) and vector time-resolved photoelectron angular distribution (TRPAD) observables were recorded during the predissociation. The TRPES yield of photoelectrons was found to oscillate with a quantum beat pattern for the photoelectrons corresponding to ionization to the vibrationless cation ground state; this beat pattern was obscured for photoelectron energies corresponding to ionization from the vibrationally excited CS2 cation. The TRPAD data was recorded for two general molecular ensemble cases: with and without a pre-excitation alignment laser pulse. It was found that in the case of ensemble alignment (Chapter 6), the “molecular frame” TRPAD (i.e. TRMFPAD) was able to image the purely valence electronic dynamics of the evolving CS2 C-state. The unaligned ensemble TRPAD observable suffers from excessive orientational averaging and was unable to observe the quantum beat. Engineering efforts were also undertaken to eliminate scattered light background signal (Chapter 7, Appendix A) and improve laser stability as a function of ambient pressure (Appendix B) for TRMFPAD experiments.
Thesis (Ph.D, Chemistry) -- Queen's University, 2012-09-11 22:18:20.89