Simulations of charge transport in organic compounds

To aid the design of organic semiconductors, we study the charge transport properties of organic liquid crystals, i.e. hexabenzocoronene and carbazole macrocycle, and single crystals, i.e. rubrene, indolocarbazole and benzothiophene derivatives (BTBT, BBBT). The aim is to find structure-property relationships linking the chemical structure as well as the morphology with the bulk charge carrier mobility of the compounds. To this end, molecular dynamics (MD) simulations are performed yielding realistic equilibrated morphologies. Partial charges and molecular orbitals are calculated based on single molecules in vacuum using quantum chemical methods. The molecular orbitals are then mapped onto the molecular positions and orientations, which allows calculation of the transfer integrals between nearest neighbors using the molecular orbital overlap method. Thus we obtain realistic transfer integral distributions and their autocorrelations. In case of organic crystals the differences between two descriptions of charge transport, namely semi-classical dynamics (SCD) in the small polaron limit and kinetic Monte Carlo (KMC) based on Marcus rates, are studied. The liquid crystals are investigated solely in the hopping limit. To simulate the charge dynamics using KMC, the centers of mass of the molecules are mapped onto lattice sites and the transfer integrals are used to compute the hopping rates. In the small polaron limit, where the electronic wave function is spread over a limited number of neighboring molecules, the Schroedinger equation is solved numerically using a semi-classical approach. The results are compared for the different compounds and methods and, where available, with experimental data. The carbazole macrocycles form columnar structures arranged on a hexagonal lattice with side chains facing inwards, so columns can closely approach each other allowing inter-columnar and thus three-dimensional transport. When taking only intra-columnar transport into account, the mobility is orders of magnitude lower than in the three-dimensional case. BTBT is a promising material for solution-processed organic field-effect transistors. We are able to show that, on the time-scales of charge transport, static disorder due to slow side chain motions is the main factor determining the mobility. The resulting broad transfer integral distributions modify the connectivity of the system but sufficiently many fast percolation paths remain for the charges. Rubrene, indolocarbazole and BBBT are examples of crystals without significant static disorder. The high mobility of rubrene is explained by two main features: first, the shifted cofacial alignment of its molecules, and second, the high center of mass vibrational frequency. In comparsion to SCD, only KMC based on Marcus rates is capable of describing neighbors with low coupling and of taking static disorder into account three-dimensionally. Thus it is the method of choice for crystalline systems dominated by static disorder. However, it is inappropriate for the case of strong coupling and underestimates the mobility of well-ordered crystals. SCD, despite its one-dimensionality, is valuable for crystals with strong coupling and little disorder. It also allows correct treatment of dynamical effects, such as intermolecular vibrations of the molecules. Rate equations are incapable of this, because simulations are performed on static snapshots. We have thus shown strengths and weaknesses of two state of the art models used to study charge transport in organic compounds, partially developed a program to compute and visualize transfer integral distributions and other charge transport properties, and found structure-mobility relations for several promising organic semiconductors.

Synthesis and characterization of oligo(thiophene carboxamide)s

Die vorliegende Arbeit besteht aus zwei Teilen: Im ersten Teil der Arbeit werden supramolekulare Strukturen betrachtet, die durch unterschiedliche Fällungsbedingungen von Polyethylenoxid-block-oligo-p-benzamid-copolymeren erhalten wurden. Durch tropfenweise Zugabe des gelösten Polymers zu Chloroform, ein für Polyethylenoxid selektives Lösemittel, konnten verschiedenste Aggregate hergestellt werden. Von großen Hohlkugel mit einem Durchmesser von mehreren Mikrometern, bis zu kleinen Stäbchen mit den Abmessungen von zehn Nanometern in der Breite und einigen hundert Nanometern Länge, konnten beobachtet werden.rnDer Hauptteil der Arbeit handelt von der Synthese und Charakterisierung eines neuen, konjugierten Oligomers: Oligothiophencarbonsäureamid. Das hierfür nötige Monomer, eine 2-Aminothiophen-5-carbonsäure konnte mittels Gewald-Synthese, eine multikomponenten Ringschlussreaktion dargestellt werden. Diese Methode erlaubt die Herstellung von vierfach substituierten Thiophenen, wobei 3- und 4-Position meist Alkylketten und Ester sind. Das so hergestellte Material konnte in der stufenweise Synthese von Oligothiophencarbonsäureamiden genutzt werden. Die neuen Oligomere zeigten interessante Absorptions- und Fluoreszenzeigenschaften. In Dichlormethan wurde eine bathochrome Verschiebung der Absorptionsbande in Abhängigkeit der Oligomerlänge beobachtet. Das Pentamer erreichte eine Absorptionsenergie, die der Bande des Polythiophencarbonsäureamids entspricht, was bedeutetet, dass die effektive Konjugationslänge erreicht wurde. Im Gegensatz zu den Messungen in Dichlormethan, zeigten die Oligomere Aggregationstendenzen ab dem Trimer in N,N-Dimethylformamid. Die auftretende Charge-Transfer Bande verschwand mit steigenden Konzentrationen. Eine mögliche hypsochrome Verschiebung dieser Bande, deutet auf eine Bildung von H Aggregaten hin. Fluoreszenz und zeitaufgelöste Fluoreszenzmessungen ergaben die für konjugierte Systeme zu erwartenden Effekte. Die Konjugation entlang des Amids konnte ebenfalls mittels quantenmechanischer Berechnung nachgewiesen werden.

Untersuchungen zur Photophysik einzelner konjugierter Polymerketten bei tiefen Temperaturen

Die spektroskopische Untersuchung einzelner konjugierter Polymermoleküle, welche multichromophore Systeme darstellen, bei 1,2K eröffnete den Zugang zu den unterschiedlichen Chromophoren. In Fluoreszenzemissions- wie -anregungsspektren des Poly(2-methoxy-5-(2’-ethylhexyloxy)-rnp-phenylenvinylen) (MEH-PPV) konnten Nullphononenlinien (rein elektronische (0-0)-Übergänge) emittierender Chromophore beobachtet werden, deren Breiten durch das experimentelle Auflösungsvermögen limitiert waren. Dadurch konnte eine obere Grenze für die homogene Linienbreite festgelegt werden. Infolge starker linearer Elektron-Phonon-Kopplung und spektraler Diffusion war die Beobachtung von Nullphononenlinien jedoch auf eine Minderheit der Chromophorernbeschränkt. In geeigneten Probesystemen konnten in Anregungsspektren auch Nullphononenlinien solcher Chromophore identifiziert werden, die als Donoren im intramolekularen Energietransfer fungieren. Aufgrund der dadurch verkürzten Fluoreszenzlebensdauer und der damit verbundenen Linienverbreiterung erlaubte ihre Untersuchung die Ermittlung von Energietransferraten. Eine bei Proben höherer Molmasse auftretenden niederenergetische Subpopulation an Emittern wurde auf Grundlage ihres Fluoreszenzemissions-, -anregungs- und -abklingverhaltens und unter Berücksichtigung theoretischer Arbeiten auf längere chromophore Einheiten zurückgeführt, die sich infolge von Packungseffekten in geordneten Regionen der Polymerkette ausbilden. Die schwächere lineare Elektron-Phonon-Kopplung des leiterartig verknüpften Polypentaphenylen (LPPentP) äußerte sich in einer erhöhten Wahrscheinlichkeit des Auftretens von Nullphononenlinien. Die genaue Bestimmung von Energietransferraten litt allerdings unter einem weiteren signifikanten Beitrag zur Linienbreite neben der Lebensdauer des angeregten Zustandes (möglicherweisernspektrale Diffusion oder schnelle Dephasierungsprozesse).

Ein Experiment zur Bestimmung des g-Faktors des gebundenen Elektrons in wasserstoff- und lithiumähnlichen mittelschweren Ionen

In dieser Arbeit werden der experimentelle Aufbau und erste Messungen für die Bestimmung des g-Faktors des Elektrons gebunden in wasserstoff- und lithiumähnlichen mittelschweren Ionen beschrieben. Mit dem hochpräzisenWert des g-Faktors können theoretische Berechnungen der Quantenelektrodynamik gebundener Zustände überprüft werden. Die Messungen werden in einem Dreifach-Penningfallen-System durchgeführt. Dort wurden im Rahmen dieser Arbeit auch erstmals hochgeladene Ionen bis 28Si13+ in einer hierfür entwickelten Elektronenstrahl-Ionenquelle/-falle erzeugt. Für die Bestimmung des g-Faktors werden die freie Zyklotronfrequenz und die Larmorfrequenz benötigt. Erstere wird aus den drei Eigenfrequenzen des in der Präzisionsfalle gespeicherten Ions berechnet. Um das Ion bei den Messungen nicht zu verlieren, werden die Eigenfrequenzen des Ions durch Kopplung an einen radiofrequenten Nachweisschwingkreis nicht-destruktiv nachgewiesen. Die freie Zyklotronfrequenz konnte dabei mit einer relativen Genauigkeit von wenigen 10E−9 bestimmt werden. Zur Bestimmung der Larmorfrequenz ist die genaue Kenntnis der Spinrichtung des Elektrons im Magnetfeld notwendig. Diese wird durch den kontinuierlichen Stern-Gerlach-Effekt in der sogenannten Analysefalle bestimmt. Hierzu muss eine hohe Stabilität der axialen Frequenz des Ions erreicht werden. Um dies sowie die Hochpräzisionsmessungen in der Präzisionsfalle zu erreichen, wurden in dieser Arbeit beide Fallen hinsichtlich ihrer elektrischen und magnetischen Eigenschaften charakterisiert.

Contribution of Non-Covalent Interactions and Electronic Effects on the Conformational Landscape and Tautomeric Equilibria of Molecules and Molecular Complexes: Structural and Dynamical Data from Rotational Spectroscopy

This thesis concerns the study of complex conformational surfaces and tautomeric equilibria of molecules and molecular complexes by quantum chemical methods and rotational spectroscopy techniques. In particular, the focus of this research is on the effects of substitution and noncovalent interactions in determining the energies and geometries of different conformers, tautomers or molecular complexes. The Free-Jet Absorption Millimeter Wave spectroscopy and the Pulsed-Jet Fourier Transform Microwave spectroscopy have been applied to perform these studies and the obtained results showcase the suitability of these techniques for the study of conformational surfaces and intermolecular interactions. The series of investigations of selected medium-size molecules and complexes have shown how different instrumental setups can be used to obtain a variety of results on molecular properties. The systems studied, include molecules of biological interest such as anethole and molecules of astrophysical interest such as N-methylaminoethanol. Moreover halogenation effects have been investigated on halogen substituted tautomeric systems (5-chlorohydroxypyridine and 6-chlorohydroxypyridine), where it has shown that the position of the inserted halogen atom affects the prototropic equilibrium. As for fluorination effects, interesting results have been achieved investigating some small complexes where a molecule of water is used as a probe to reveal the changes on the electrostatic potential of different fluorinated compounds: 2-fluoropyridine, 3-fluoropyridine and penta-fluoropyridine. While in the case of the molecular complex between water and 2-fluoropyridine and 3-fluoropyridine the geometry of the complex with one water molecule is analogous to that of pyridine with the water molecule linked to the pyridine nitrogen, the case of pentafluoropyridine reveals the effect of perfluorination and the water oxygen points towards the positive center of the pyridine ring. Additional molecular adducts with a molecule of water have been analyzed (benzylamine-water and acrylic acid-water) in order to reveal the stabilizing driving forces that characterize these complexes.

Molecular dynamics simulations of silicate and borate glasses and melts : structure, diffusion dynamics and vibrational properties

Molecular dynamics simulations of silicate and borate glasses and melts: Structure, diffusion dynamics and vibrational properties. In this work computer simulations of the model glass formers SiO2 and B2O3 are presented, using the techniques of classical molecular dynamics (MD) simulations and quantum mechanical calculations, based on density functional theory (DFT). The latter limits the system size to about 100−200 atoms. SiO2 and B2O3 are the two most important network formers for industrial applications of oxide glasses. Glass samples are generated by means of a quench from the melt with classical MD simulations and a subsequent structural relaxation with DFT forces. In addition, full ab initio quenches are carried out with a significantly faster cooling rate. In principle, the structural properties are in good agreement with experimental results from neutron and X-ray scattering, in all cases. A special focus is on the study of vibrational properties, as they give access to low-temperature thermodynamic properties. The vibrational spectra are calculated by the so-called ”frozen phonon” method. In all cases, the DFT curves show an acceptable agreement with experimental results of inelastic neutron scattering. In case of the model glass former B2O3, a new classical interaction potential is parametrized, based on the liquid trajectory of an ab initio MD simulation at 2300 K. In this course, a structural fitting routine is used. The inclusion of 3-body angular interactions leads to a significantly improved agreement of the liquid properties of the classical MD and ab initio MD simulations. However, the generated glass structures, in all cases, show a significantly lower fraction of 3-membered planar boroxol rings as predicted by experimental results (f=60%-80%). The largest boroxol ring fraction of f=15±5% is observed in the full ab initio quenches from 2300 K. In case of SiO2, the glass structures after the quantum mechanical relaxation are the basis for calculations of the linear thermal expansion coefficient αL(T), employing the quasi-harmonic approximation. The striking observation is a change change of sign of αL(T) going along with a temperature range of negative αL(T) at low temperatures, which is in good agreement with experimental results.

Conformationally Controlled Electron Delocalization in n-Type Rods: Synthesis, Structure, and Optical, Electrochemical, and Spectroelectrochemical Properties of Dicyanocyclophanes

A series of dicyanobiphenyl-cyclophanes 1-6 with various pi-backbone conformations and characteristic n-type semiconductor properties is presented. Their synthesis, optical, structural, electrochemical, spectroelectrochemical, and packing properties are investigated. The X-ray crystal structures of all n-type rods allow the systematic correlation of structural features with physical properties. In addition, the results are supported by quantum mechanical calculations based on density functional theory. A two-step reduction process is observed for all n-type rods, in which the first step is reversible. The potential gap between the reduction processes depends linearly on the cos(2) value of the torsion angle phi between the pi-systems. Similarly, optical absorption spectroscopy shows that the vertical excitation energy of the conjugation band correlates with the cos(2) value of the torsion angle phi. These correlations demonstrate that the fixed intramolecular torsion angle phi is the dominant factor determining the extent of electron delocalization in these model compounds, and that the angle phi measured in the solid-state structure is a good proxy for the molecular conformation in solution. Spectroelectrochemical investigations demonstrate that conformational rigidity is maintained even in the radical anion form. In particular, the absorption bands corresponding to the SOMO-LUMO+i transitions are shifted bathochromically, whereas the absorption bands corresponding to the HOMO-SOMO transition are shifted hypsochromically with increasing torsion angle phi.

Theoretical estimation of optical absorption and photoluminescence in nanostructured silicon; an approach to improve efficiency in nanostructured solar cells

Renewable energy is growing in demand, and thus the the manufacture of solar cells and photovoltaic arrays has advanced dramatically in recent years. This is proved by the fact that the photovoltaic production has doubled every 2 years, increasing by an average of 48% each year since 2002. Covering the general overview of solar cell working, and its model, this thesis will start with the three generations of photovoltaic solar cell technology, and move to the motivation of dedicating research to nanostructured solar cell. For the current generation solar cells, among several factors, like photon capture, photon reflection, carrier generation by photons, carrier transport and collection, the efficiency also depends on the absorption of photons. The absorption coefficient,α, and its dependence on the wavelength, λ, is of major concern to improve the efficiency. Nano-silicon structures (quantum wells and quantum dots) have a unique advantage compared to bulk and thin film crystalline silicon that multiple direct and indirect band gaps can be realized by appropriate size control of the quantum wells. This enables multiple wavelength photons of the solar spectrum to be absorbed efficiently. There is limited research on the calculation of absorption coefficient in nano structures of silicon. We present a theoretical approach to calculate the absorption coefficient using quantum mechanical calculations on the interaction of photons with the electrons of the valence band. One model is that the oscillator strength of the direct optical transitions is enhanced by the quantumconfinement effect in Si nanocrystallites. These kinds of quantum wells can be realized in practice in porous silicon. The absorption coefficient shows a peak of 64638.2 cm-1 at = 343 nm at photon energy of ξ = 3.49 eV ( = 355.532 nm). I have shown that a large value of absorption coefficient α comparable to that of bulk silicon is possible in silicon QDs because of carrier confinement. Our results have shown that we can enhance the absorption coefficient by an order of 10, and at the same time a nearly constant absorption coefficient curve over the visible spectrum. The validity of plots is verified by the correlation with experimental photoluminescence plots. A very generic comparison for the efficiency of p-i-n junction solar cell is given for a cell incorporating QDs and sans QDs. The design and fabrication technique is discussed in brief. I have shown that by using QDs in the intrinsic region of a cell, we can improve the efficiency by a factor of 1.865 times. Thus for a solar cell of efficiency of 26% for first generation solar cell, we can improve the efficiency to nearly 48.5% on using QDs.

Modern charge density studies: the entanglement of experiment and theory

This tutorial review article is intended to provide a general guidance to a reader interested to learn about the methodologies to obtain accurate electron density mapping in molecules and crystalline solids, from theory or from experiment, and to carry out a sensible interpretation of the results, for chemical, biochemical or materials science applications. The review mainly focuses on X-ray diffraction techniques and refinement of experimental models, in particular multipolar models. Neutron diffraction, which was widely used in the past to fix accurate positions of atoms, is now used for more specific purposes. The review illustrates three principal analyses of the experimental or theoretical electron density, based on quantum chemical, semi-empirical or empirical interpretation schemes, such as the quantum theory of atoms in molecules, the semi-classical evaluation of interaction energies and the Hirshfeld analysis. In particular, it is shown that a simple topological analysis based on a partition of the electron density cannot alone reveal the whole nature of chemical bonding. More information based on the pair density is necessary. A connection between quantum mechanics and observable quantities is given in order to provide the physical grounds to explain the observations and to justify the interpretations.

Keeping Mars warm with new super greenhouse gases

Our selection of new super greenhouse gases to fill a putative “window” in a future Martian atmosphere relies on quantum-mechanical calculations. Our study indicates that if Mars could somehow acquire an Earth-like atmospheric composition and surface pressure, then an Earth-like temperature could be sustained by a mixture of five to seven fluorine compounds. Martian mining requirements for replenishing the fluorine could be comparable to current terrestrial extraction.

Dinâmica molecular de sistemas iônicos poliatômicos: modelos polarizável e não-polarizável

Simulações de sais de carbonato fundidos pelo método de Dinâmica Molecular (MD) foram efetuadas com o modelo polarizável de cargas flutuantes (FC). O modelo de cargas flutuantes implementa os efeitos de polarização pelo método de Lagrangiano estendido, onde as variáveis extras são as próprias cargas parciais do íon poliatômico. O modelo FC foi parametrizado por meio de cálculos ab inito, aplicado ao ânion carbonato. Cálculos de Química Quântica ab initio foram utilizados para corroborar o modelo proposto para o ânion carbonato. Os sistemas investigados consistem em misturas de carbonatos alcalinos fundidos, Li2CO3/K2CO3, os quais são utilizados como eletrólitos em células a combustível. As simulações MD foram utilizadas para verificar o efeito da polarização dos ânions sobre a estrutura e dinâmica do líquido. Estudamos o efeito da inclusão de polarização sobre a condutividade do eletrólito.

Electronic structure and transport properties of atomic NiO spinvalves

Ab initio quantum transport calculations show that short NiO chains suspended in Ni nanocontacts present a very strong spin-polarization of the conductance.The generalized gradient approximation we use here predicts a similar polarization of the conductance as the one previously computed with non-local exchange, confirming the robustness of the result. Their use as nanoscopic spinvalves is proposed.

Spin alignment of extra electrons in K-phenanthrene clusters taken from the crystalline tripotassium-intercalated phenanthrene structure

The appearance of ferromagnetic correlations among π electrons of phenanthrene (C14H10) molecules in the herringbone structure is proven for K doped clusters both by ab initio quantum-chemistry calculations and by the direct solution of the many-body Pariser-Parr-Pople Hamiltonian. Magnetic ground states are predicted for one or three additional electrons per phenanthrene molecule. These results are a consequence of the small overlap between the lowest unoccupied molecular orbitals (and lowest unoccupied molecular orbitals + 1) of neutral neighboring phenanthrene molecules, which makes the gain in energy by delocalization similar to the corresponding increase due to the Coulomb interaction.

Understanding the structure of the first atomic contact in gold

We have studied experimentally jump-to-contact (JC) and jump-out-of-contact (JOC) phenomena in gold electrodes. JC can be observed at first contact when two metals approach each other, while JOC occurs in the last contact before breaking. When the indentation depth between the electrodes is limited to a certain value of conductance, a highly reproducible behaviour in the evolution of the conductance can be obtained for hundreds of cycles of formation and rupture. Molecular dynamics simulations of this process show how the two metallic electrodes are shaped into tips of a well-defined crystallographic structure formed through a mechanical annealing mechanism. We report a detailed analysis of the atomic configurations obtained before contact and rupture of these stable structures and obtained their conductance using first-principles quantum transport calculations. These results help us understand the values of conductance obtained experimentally in the JC and JOC phenomena and improve our understanding of atomic-sized contacts and the evolution of their structural characteristics.

Gymnoascolides A-C: Aromatic butenolides from an Australian isolate of the soil ascomycete Gymnoascus reessii

Three new aromatic butenolides, gymnoascolides A-C (1-3), have been isolated from the Australian soil ascomycete Gymnoascus reessii and assigned structures on the basis of detailed spectroscopic analysis. The absolute configurations of gymnoascolides B (2) and C (3) at C-5 were solved using a combination of chemical derivatization and quantum chemical simulations.