From a theoretical standpoint, the accurate description of potential energy surfaces for bond breaking and the equilibrium structures of metal-ligand catalysts are distinctly similar problems. Near degeneracies of the bonding and anti-bonding orbitals for the case of bond breaking and of the partially-filled d-orbitals for the case of metal-ligand catalyst systems lead to strong non-dynamical correlation effects. Standard methods of electronic structure theory, as a consequence of the single-reference approximation, are incapable of accurately describing the electronic structure of these seemingly different theoretical problems. The work within highlights the application of multi-reference methods, methods capable of accurately treating these near-degeneracies, for describing the bond-breaking potentials in several small molecular systems and the equilibrium structures of metal-salen catalysts. The central theme of this work is the ability of small, compact reference functions for accurately describing the strong non-dynamical correlation effects in these systems.

Das Forschungsgebiet der Kuprat- oder Hochtemperatursupraleiter (HTSL) ist bis heute einer der lebendigsten Bereiche der Physik kondensierter Materie. Ein besonderer Stellenwert kommt dem normalleitenden Zustand oberhalb TC zu, dessen Verständnis wesentlich zu einer Theorie der Hochtemperatur-Supraleitung beitragen könnte. Gegenstand dieser Arbeit ist die Untersuchung der Elektronenstruktur von HTSLn der Bi2Sr2CaCu2O8+[delta](Bi2212)-Familie nahe der Fermifläche im normalleitenden Zustand. Die Experimente wurden mittels winkelaufgelöster Photoemissionsspektroskopie (ARPES) durchgeführt, wobei die hohe Auflösung in Energie und Impuls recht genaue Rückschlüsse auf die Spektralfunktion und die Übergangs-Matrixelemente erlaubt. Die wichtigsten experimentellen Ergebnisse sind: 1) Hochaufgelöste ARPES-Fermiflächenkarten von Bi2212 und (Pb,Bi)2212 zeigen folgendes Bild: Die Hauptfermifläche ist lochartig und um die Ecken der Brillouinzone zentriert. Weiterer Bestandteil der Elektronenstruktur ist die Schattenfermifläche. Bei reinem Bi2212 treten außerdem extrinsische Beugungskopien der Fermifläche auf. 2) ARPES-Messungen entlang der -M-Richtung von Bi2212 zeigen eine starke Abhängigkeit von der Anregungsenergie, die auf starken Matrixelement-Effekten beruht. Verschiedene Methoden zur Bestimmung von kF zeigen, dass die Daten konsistent mit einer lochartigen Topologie der Hauptfermifläche sind. Des Weiteren wird die Qualität verschiedener Methoden zur Bestimmung von kF bei starken Matrixelement-Effekten bewertet. 3) Die Hauptfermifläche von (Pb,Bi)2212 behält ihre lochartige Topologie über einen großen Dotierungsbereich nahe optimaler Dotierung. 4) Erste hochaufgelöste ARPES-Messungen des Zirkulardichroismus wurden an (Pb,Bi)2212 durchgeführt. In der verwendeten nicht-chiralen Messanordnung wird ein CDAD (Circular Dichroism in the Angular Distribution of Photoelectrons)-Effekt beobachtet, dessen Asymmetrie antisymmetrisch bezüglich der Zweischicht-aufgespaltenen Zustände ist.

The discovery of an unexpectedly large thermopower accompanied by low resistivity and low thermal conductivity in NaxCoO2 raised significant research interest in these materials and let to a number of experimental and theoretical investigations. This interest has strongly been reinforced by the discovery of superconductivity in the hydrated compound Na0.35CoO2 •1.3H2O in 2003, and thus, NaxCoO2 experiences an again increasing attention. The similarity of the Na cobaltates to the high temperature superconductors (HTSC) - both are transition metal oxides and adopt a layered crystal structure with quasi-two-dimensional (Cu,Co)O2 layers - is an important aspect of the research activities. In contrast to the HTSC cuprates however, the CoO2 layers consist of edge sharing CoO6 octahedra which are distorted in such a way that the resulting local symmetry is trigonal. The trigonal coordination of the Co sites results in geometric frustration which favours unconventional electronic ground states. The geometrically frustrated CoO2 sublattice also exists in the nonhydrated parent compound NaxCoO2, which has been investigated in this work. The intercalation of water into the parent compound is expected to have little effect on the Fermi surface beside the increase in two dimensionality due to the effect of expansion. Upon lowering the symmetry from cubic to trigonal, the t2g states split into states with eg_and a1g symmetry. Measurements of polarisation and temperature dependent soft X-ray absorption have been performed on a wide doping range of NaxCoO2 single crystals. Beside the Co L_2,3-edges, the O K-edge and the Na K-edge have been measured. These measurements show strong polarisation dependencies especially for the excitations into the lower lying a1g energy level. In addition to that, also an unexpected polarisation dependence for higher energies has been observed, which should be absent in trigonal symmetry. These results point towards a deviation of the local trigonal symmetry of the CoO6 octahedra, which is temperature independent in a temperature range between 25 K and 372 K. This deviation was found to be different for Co3+ and Co4+ sites, which leads to a polaronic electron transport. Furthermore, a strong hybridisation between the Co and O ions has been found. In order to shed further light on the electronic structure of NaxCoO2, the electronic spectrum of a CoO6 cluster has been calculated including all interactions between 3d orbitals as well as hopping processes between Co and O and O and O ions. The ground state for two electronic occupations in the cluster (i.e. Co3+ and Co4+) that correspond nominally to all O in the O−2 oxidation state, and Co+3 or Co+4 has been obtained. Then, all excited states obtained by promotion of a Co 2p electron to a 3d electron, and the corresponding matrix elements are calculated. A fit of the observed experimental spectra is good and points out a large Co-O covalence and cubic crystal field effects, that result in low spin Co 3d configurations. The results indicate that the effective hopping between different Co atoms plays a major role in determining the symmetry of the ground state in the lattice. Remaining quantitative discrepancies with the XAS experiments are expected to come from composition effects of itineracy in the ground and excited states. Beside these points, results of photoemission spectroscopy, magnetisation measurements as well as resonant and non-resonant X-ray diffraction using high energy X-rays are shown and discussed. / Die Entdeckung unerwartet großer Thermokraft bei gleichzeitigem niedrigem Widerstand und niedriger thermischen Leitfähigkeit in NaxCoO2 führte zu einem großen wissenschaftlichem Interesse an diesen Materialien und zu einer großen Anzahl an experimentellen und theoretischen Arbeiten. Dieses Interesse steigerte sich noch einmal nach der Entdeckung von Supraleitung in der hydrierten Verbindung Na0.35CoO2 •1.3H2O im Jahre 2003. Die Ähnlichkeit der Na Kobaltate zu den Hochtemperatur-Supraleitern (HTSL) – beides sind Übergangsmetalloxide mit einer geschichteten Kristallstruktur in der quasi zwei dimensionale (Cu,Co)O2 Ebenen enthalten sind – ist ein wichtiger Aspekt moderner wissenschaftlicher Arbeiten. Im Gegensatz zu den HTSL Kupraten bestehen die CoO2 Ebenen aus CoO6 Oktaedern die über ihre Kanten verbunden sind und in der Art verzerrt sind, dass die resultierende Symmetrie trigonal ist. Die trigonale Anordnung der Co Plätze führt zu einer geometrischen Frustration und unkonventionellen elektronischen Grundzuständen. Diese geometrisch frustrierten CoO2 Untergitter existieren ebenfalls in den nicht hydrierten Mutterverbindungen NaxCoO2, welche in dieser Arbeit untersucht wurden. Interkalierung von Wasser in die Mutterverbindung hat nur einen kleinen Einfluss auf die Fermi Oberfläche und führt zu einem Anstieg des zwei dimensionalen Charakters durch den Effekt der Ausdehnung. Durch Verminderung der Symmetrie von kubisch zu trigonal splitten die vormals entarteten t2g Zustände auf in Zustände mit eg und a1g Symmetrie. Zur Bestimmung der elektronischen Struktur von NaxCoO2 wurden polarisations- und temperaturabhängige Messungen der Röntgenabsorption im weichen Röntgenbereich für einen großen Dotierungsbereich durchgeführt. Neben den Co L_2,3-Kanten wurden auch die O K-Kante und die Na K-Kante gemessen. Sie zeigen eine starke Polarisationsabhängigkeit speziell für Anregungen in die niederenergetischen a1g Level. Zusätzlich wurde eine unerwartete Polarisationsabhängigkeit bei höheren Energien gefunden, die für trigonalen Symmetrie so nicht auftauchen dürfte. Diese Ergebnisse weisen auf eine Abweichung von der lokalen trigonalen Symmetrie der CoO6 Oktaeder hin, welche Temperatur unabhängig ist in einem Temperaturbereich zwischen 25 und 372 Kelvin. Diese Abweichung ist unterschiedlich für Co3+ und Co4+ Ionen was wiederum auf einen polaronischen Transport hinweist. Zusätzlich wird deutlich, dass eine starke Co-O Hybridisierung existieren muss. Um weiteres Informationen über die elektronische Struktur von NaxCoO2 zu erhalten, wurde das elektronische Spektrum eines CoO6 Oktaeders berechnet in dem alle Wechselwirkungen zwischen 3d Orbitalen sowie Hüpfprozesse zwischen Co und O sowie O und O Ionen enthalten sind. Der Grundzustand für zwei elektronische Besetzungen in einem Cluster (d.h. Co3+ und Co4+) wurde bestimmt für O Ionen mit einer nominellen O-2 Oxidation sowie Co3+ und Co4+ Ionen. Im angeregten Zustand werden die entsprechenden Anregungen eines Co 2p Elektrons in einen unbesetzten 3d Zustand berücksichtigt und die entsprechenden Matrixelemente berechnet. Ein Fit an den experimentellen Daten ist gut und weist auf eine starke Co-O Kovalenz und auf einen starken Einfluss des kubischen Kristallfeldes hin, der zu einer Low-Spin Co 3d Konfiguration führt. Die Ergebnisse zeigen, dass ein effektives Hüpfen zwischen benachbarter Co Ionen eine große Rolle für die Symmetrie des Grundzustandes im Gitter spielt. Quantitative Unterschiede zwischen den experimentellen und theoretischen Daten kommen anscheinend von itineranten Effekten im Grund- und angeregten Zustand. Zusätzlich zu den oben kurz beschriebenen Ergebnissen werden in dieser Arbeit weitere Ergebnisse der Photoemissionsspektroskopie, der Magnetisierung sowie aus resonanter und nicht resonanter Röntgenbeugung mit harter Röntgenstrahlung gezeigt und diskutiert.

Computational approaches play an important role in today's materials science owing to the remarkable advances in modern supercomputing architecture and algorithms. Ab initio simulations solely based on a quantum description of matter are now very able to tackle materials problems in which the system contains up to a few thousands atoms. This dissertation aims to address the modern electronic structure calculation methods applied to a range of various materials such as liquid and amorphous phase materials, nanostructures, and small organic molecules. Our simulations were performed within the density functional theory framework, emphasizing the use of real-space ab initio pseudopotentials. On the first part of our study, we performed liquid and amorphous phase simulations by employing a molecular dynamics technique accelerated by a Chebyshev-subspace filtering algorithm. We applied this technique to find l- and a- SiO₂ structural properties that were in a good agreement with experiments. On the second part, we studied nanostructured semiconducting oxide materials, i.e., SnO₂ and TiO₂, focusing on the electronic structures and optical properties. Lastly, we developed an efficient simulation method for non-contact atomic force microscopy. This fast and simple method was found to be a very powerful tool for predicting AFM images for many surface and molecular systems. / text

Vad karaktäriserar en kristall? Svaret på denna till synes enkla fråga blir kanske att det är en anordning av atomer uppradade i periodiska mönster. Så ordnade strukturer kan studeras genom att det uppträder så kallade Braggtoppar i röntgendiffraktionsmönstret. Om frågan gäller elektrontäthetsfördelningen, kanske svaret blir att denna är periodisk och grundar sig på elektronvågor som genomtränger hela kristallen. I och med att nya typer av ordnade system, så kallade kvasikristaller, upptäcks och framställs på artificiell väg blir svaren på dessa frågor mer intrikata. En kristall behöver inte bestå av enheter upprepade periodiskt i rummet, och den klassiska metoden att karaktärisera strukturer via röntgendiffraktionsmönstret kanske inte alls är den allena saliggörande. I denna avhandling visas att ett ordnat gitter vars röntgendiffraktionsmönster saknar inre struktur, dvs är av samma diffusa typ som vad ett oordnat material uppvisar, fortfarande kan ha elektronerna utsträckta över hela strukturen. Detta implicerar att det inte finns något enkelt samband mellan diffraktionsmönstret från gittret och dess fysikaliska egenskaper såsom t ex lokalisering av vågfunktionerna. Man talar om lokalisering när en vågfunktion är begränsad inom en del av materialet och inte utsträckt över hela dess längd, vilket är av betydelse när man vill avgöra huruvida ett material är en isolator, halvledare eller ledare. Det vittnar samtidigt om behovet av att söka efter andra karakteristika när man försöker beskriva skillnaden mellan ett ordnat och ett oordnat material, där den senare kategorin kan uppvisa lokalisering. Resultaten utgör en klassificering av det svåröverskådliga området aperiodiska gitter i en dimension. Det leder till hypotesen att ideala kvasikristaller, genererade med bestämda regler, har kontinuerligt energispektrum av fraktal natur. I reella material spelar korrelation en viktig roll. Vid icke-linjär återkoppling till gittret kan man erhålla intrinsiskt lokaliserade vågor, som i många avseenden beter sig som partiklar, solitoner, vilka har visat sig ha viktiga tillämpningar inom bl a optisk telekommunikation. Sådana vågors roll for lagring och transport av energi har undersökts i teoretiska modeller for optiska vågledare och kristaller där ljuset har en förmåga att manipulera sig självt. / Spectral and dynamical properties of electrons, phonons, electromagnetic waves, and nonlinear coherent excitations in one-dimensional modulated structures with long-range correlations are investigated from a theoretical point of view. First a proof of singular continuous electron spectrum for the tight-binding Schrödinger equation with an on-site potential, which, in analogy with a random potential, has an absolutely continuous correlation measure, is given. The critical behavior of such a localization phenomenon manifests in anomalous diffusion for the time-evolution of electronic wave packets. Spectral characterization of elastic vibrations in aperiodically ordered diatomic chains in the harmonic approximation is achieved through a dynamical system induced by the trace maps of renormalized transfer matrices. These results suggest that the zero Lebesgue measure Cantor-set spectrum (without eigenvalues) of the Fibonacci model for a quasicrystal is generic for deterministic aperiodic superlattices, for which the modulations take values via substitution rules on finite sets, independent of the correlation measure. Secondly, a method to synthesize and analyze discrete systems with prescribed long-range correlated disorder based on the conditional probability function of an additive Markov chain is effectively implemented. Complex gratings (artificial solids) that simultaneously display given characteristics of quasiperiodic crystals and amorphous solids on the Fraunhofer diffraction are designated. A mobility edge within second order perturbation theory of the tight-binding Schrödinger equation with a correlated disorder in the dichotomic potential realizes the success of the method in designing window filters with specific spectral components. The phenomenon of self-localization in lattice dynamical systems is a subject of interest in various physical disciplines. Lattice solitons are studied using the discrete nonlinear Schrödinger equation with on-site potential, modeling coherent structures in, for example, photonic crystals. The instability-induced dynamics of the localized gap soliton is found to thermalize according to the Gibbsian equilibrium distribution, while the spontaneous formation of persisting intrinsic localized modes from the extended out-gap soliton reveals a phase transition of the solution.

科学研究費補助金 研究種目:研究(A)(1) 課題番号:07555500 研究代表者:森永 正彦 研究期間:1995-1996年度

Designing novel nanostructures which exploit the self-assembly capabilities of biomolecules yields a promising approach to control matter at the nanoscale. Here, the homochiral molecular self-assemblies of the methionine and tyrosine amino acids on the monocrystalline Ag(111) and Cu(111) surfaces are characterized by means of scanning tunneling microscopy (STM) and spectroscopy (STS), helium atom scattering (HAS), x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) in ultrahigh vacuum (UHV). On Ag(111), methionine self-assembles into supramolecular chains following the <110> substrate axis, forming regular nanogratings with tunable periodicity. Within the nanowires, a zwitterionic dimerization scheme is revealed. STS shows that the biomolecular nanostructures act as tunable one-dimensional quantum resonators for the surface state electrons. Zero-dimensional electronic confinement is achieved by positioning single iron atoms in the molecular trenches. This shows a novel approach to control the dimensionality of surface state electrons. The nanogratings were exploited to steer the spontaneous one-dimensional ordering of cobalt and iron atoms. For T > 15 K, the metal species self-align into homogeneously distributed chains in between the biomolecular trenches with ~25 Å interatomic distace. For Co, the dynamics of the self-alignment was monitored, revealing a reduced mobility in comparison with isolated Co atoms on bare Ag(111). On Cu(111), the self-assembly of methionine is influenced by the substrate reactivity and its temperature during molecular deposition. For T < 273 K, the biomolecules assemble in anisotropic extended clusters oriented with a -10° rotation off the <110> substrate orientations, whereas above 283 K a regularly ordered 1D phase arises with a +10° rotation off these high-symmetry axis. XPS reveals a structural transformation triggered by a thermally activated deprotonation of the zwitterionic ammonium group. On Ag(111), tyrosine self-assembles above a critical temperature into linear structures primarily following the substrate crystalline symmetry. A zwitterionic non-covalent molecular dimerization is demonstrated, NEXAFS data providing evidence of a non-flat adsorption of the phenyl ring. This recalls the geometrical pattern of methionine on Ag(111) and supports a universal self-assembling scheme for amino acids on close-packed noble metal surfaces, the different mesoscopic ordering being determined by the side chain reactivity.

Saviformuojantys puslaidininkiniai kvantiniai taškai (quantum dots, QDs), kurių charakteringos elektronų subjuostinių (intraband) šuolių energijos yra infraraudonajame spektriniame ruože (3–25 μm), sudaro daugelio fotojutiklių aktyviąją terpę ir yra aktualūs taikymams šiuolaikinėje optoelektronikoje. Disertacijoje nagrinėjami molekulinio pluoštelio epitaksijos būdu užauginti: -- InAs kvantiniai taškai, įterpti į GaAs matricą ir GaAs/AlAs supergardelę; -- InAs kvantiniai taškai be ir su įtempimus sumažinančiuoju InGaAs sluoksniu, įterpti į kompozitinę GaAs/AlAs kvantinę duobę; -- skirtingo aukščio koloniniai InGaAs kvantiniai taškai arba kvantiniai strypeliai (quantum rods, QRs), apsupti dvimačiu InGaAs sluoksniu, ir užauginti naudojant arba As2, arba As4 šaltinį. Taikant moduliacinę atspindžio spektroskopiją ir fotoliuminescenciją, buvo ištirtos šių darinių optinės savybės bei jų elektroninė sandara, o taip pat atskleista auginimo sąlygų įtaka darinių struktūrai. Eksperimentiniai tyrimai buvo interpretuojami atliekant teorinį modeliavimą skaitmeniniu (nextnano3 programa) bei analitiniu (sukurtas algoritmas) metodais. / Self-assembled InAs quantum dots (QDs), whose intersublevel transition energies lie in the mid- and far-infrared spectral range (3–25μm), have attracted particular interest as active elements of infrared photodetectors. This interest is mainly due to intriguing atomic-like quantum confinement and unique optical and electronic properties of QDs. Moreover, QD electronic structure can be adjusted by varying the dots size and shape or their environment. These features make QDs to be of importance in creation of photoelectronic devices with a desired spectral range. The dissertation is concerned specifically with molecular beam epitaxy grown InGaAs QD structures with: -- InAs QD stacks embedded in GaAs matrix and GaAs/AlAs superlattice (SL), or alternatively InAs/GaAs QD-SL structures with and without AlAs barriers between the dot layers; -- InAs QDs with and without InGaAs strain-reducing layers, embedded within GaAs/AlAs quantum wells; -- columnar InGaAs QDs, also referred to as quantum rods (QRs) or quantum posts, of different morphology. (The quantum confined structure consists of vertically oriented InGaAs QRs immersed in a two-dimensional InGaAs layer). These QD structures were studied by modulated reflectance and photo- luminescence spectroscopies to reveal their optical properties and the full- extent of electronic structure. Experimental data were interpreted by numerical (nextnano3 software) and analytical (algorithm developed) modelling.

Le sujet de ce mémoire est l’étude ab initio des nanotubes de carbone. Premièrement, une introduction du sujet est présentée. Elle porte sur l’historique, la structure géométrique et électronique et les applications possibles des nanotubes de carbone. En deuxième lieu, la stabilité énergétique des nanotubes de carbones double parois ainsi que leur structure électronique sont étudiées. On trouve entre autres que le changement d’hybridation provoque une chute de l’énergie du dernier niveau occupé pour les petits nanotubes. Troisièmement, nous présenterons une étude sur la dépendance en diamètre et en métallicité du greffage d’unité bromophényle sur la surface des nanotubes. La principale conclusion est qu’il est plus facile de fonctionnaliser les nanotubes de petit diamètre puisque ceux-ci ont déjà une partie d’hybridation sp3 dans leur structure électronique. Finalement, le dernier chapitre aborde la combustion des nanotubes par le dioxyde de carbone. On constate que cette combustion ne peut pas débuter sur une surface intacte, ni par un pontage d’oxygène dû à la grande quantité d’énergie requise. La réaction privilégiée est alors la combustion par les extrémités du nanotube. Nous proposons une dynamique de réaction qui contient une sélectivité en diamètre. / The subject of this master’s thesis is the ab initio study of carbon nanotubes. First, an introduction to the subject is presented. It covers the history, the geometric and electronic structure and potential applications of carbon nanotubes. Second, the energy stability of double-walled carbon nanotubes and their electronic structure are studied. It is found that the change of hybridization causes a lowering in the energy of the highest occupied molecular orbital’s level for small nanotubes. Thirdly, a study of the diameter and metallicity dependence for the bromophenyl bonding energy on the carbon nanotubes is presented. The main conclusion is that it is easier to functionalize the nanotubes of small diameter since they already have some sp3 hybridization in their electronic structure. Finally, the last chapter discusses the burning of carbon nanotubes with carbon dioxide. It is found that combustion can not begin on a pristine surface or by a oxygen bridge due to the large amount of energy required. The favored reaction is then burning the ends of nanotubes. We suggest a path of reaction for which a diameter selectivity is apparent.

The research presented in this thesis concerns experimental studies of thin manganese silicide and germanide layers, grown by solid phase epitaxy on the Si(111)7×7 and the Ge(111)c(2×8) surfaces, respectively. The atomic and electronic structures, as well as growth modes of the epitaxial Mn-Si and Mn-Ge layers, were investigated by low-energy electron diffraction (LEED), angle-resolved photoelectron spectroscopy (ARPES), core-level spectroscopy (CLS), and scanning tunneling microscopy and spectroscopy (STM and STS). The magnetic properties of the Mn-Ge films were investigated by X-ray magnetic circular dichroism (XMCD). The Mn-Si layers, annealed at 400 °C, showed a √3×√3 LEED pattern, consistent with the formation of the stoichiometric monosilicide MnSi. Up to 4 monolayers (ML) of Mn coverage, island formation was observed. For higher Mn coverages, uniform film growth was found. Our results concerning morphology and the atomic and electronic structure of the Mn/Si(111)-√3×√3 surface, are in good agreement with a recent theoretical model for a layered MnSi structure and the √3×√3 surface structure. Similar to the Mn-Si case, the grown Mn-Ge films, annealed at 330 °C and 450 °C, showed a √3×√3 LEED pattern. This indicated the formation of the ordered Mn5Ge3 germanide. A strong tendency to island formation was observed for the Mn5Ge3 films, and a Mn coverage of about 32 ML was needed to obtain a continuous film. Our STM and CLS results are in good agreement with the established model for the bulk Mn5Ge3 germanide, with a surface termination of Mn atoms arranged in a honeycomb pattern. Mn-Ge films grown at a lower annealing temperature, 260 °C, showed a continuous film at lower coverages, with a film structure that is different compared to the structure of the Mn5Ge3 film. XMCD studies showed that the low-temperature films are ferromagnetic for 16 ML Mn coverage and above, with a Curie temperature of ~250 K.