No description available.

No description available.

A hybrid molecular dynamics/multiparticle collision dynamics algorithm was constructed to model the pressure-driven flow of a compressible fluid through a nanoscopic channel of square cross-sectional area, as well as the effect of this flow on the configuration of a polymer chain that was tethered to the surface of this nanochannel. In the process of simulating channel flow, a new adiabatic partial slip boundary condition was created as well as a modified source/sink inlet and outlet boundary condition that could maintain a specified pressure gradient across the channel without the large entrance effects typically associated with these algorithms. The results of the flow simulations were contrasted with the results from a series solution to the Navier-Stokes equation for isothermal compressible flow, and showed excellent agreement with the results from the series solution when slip-boundary conditions were applied. A finitely extendible non-linear elastic spring and bead polymer chain was used to simulate the effect of flow on the polymer chain configuration under poor solvent and θ solvent conditions. Under θ solvent conditions, the cyclical dynamics that have been previousy observed for tethered polymer chains in pure shear flows were noted, however they were restricted to the end of the polymer chain. Under poor solvent conditions, the polymer adopted a metastable helix configuration as it collapsed to a globule state. The study also examined interchain and intrachain entanglements in polymers using the granny knot and overhand knot. The mechanisms by which these tangles untied themselves were determined. At low flow rates, the tangles unravelled by the end of the chain migrating through the loops of the tangle. At high flow rates, the tangles behaved like an entrained object as they reptated towards the end of the chain.

A hybrid molecular dynamics/multiparticle collision dynamics algorithm was constructed to model the pressure-driven flow of a compressible fluid through a nanoscopic channel of square cross-sectional area, as well as the effect of this flow on the configuration of a polymer chain that was tethered to the surface of this nanochannel. In the process of simulating channel flow, a new adiabatic partial slip boundary condition was created as well as a modified source/sink inlet and outlet boundary condition that could maintain a specified pressure gradient across the channel without the large entrance effects typically associated with these algorithms. The results of the flow simulations were contrasted with the results from a series solution to the Navier-Stokes equation for isothermal compressible flow, and showed excellent agreement with the results from the series solution when slip-boundary conditions were applied. A finitely extendible non-linear elastic spring and bead polymer chain was used to simulate the effect of flow on the polymer chain configuration under poor solvent and θ solvent conditions. Under θ solvent conditions, the cyclical dynamics that have been previousy observed for tethered polymer chains in pure shear flows were noted, however they were restricted to the end of the polymer chain. Under poor solvent conditions, the polymer adopted a metastable helix configuration as it collapsed to a globule state. The study also examined interchain and intrachain entanglements in polymers using the granny knot and overhand knot. The mechanisms by which these tangles untied themselves were determined. At low flow rates, the tangles unravelled by the end of the chain migrating through the loops of the tangle. At high flow rates, the tangles behaved like an entrained object as they reptated towards the end of the chain.

This dissertation examines the motion of colloids in a temperature gradient, a non-equilibrium phenomenon also known as thermophoresis. Chapter 1 gives an introduction to the existing applications and basic concepts of thermophoresis and outlines some of the experimental and theoretical challenges that serve as a motivation for this PhD project. In Chapter 2, a general theoretical description for thermophoresis is formulated using the theory of non-equilibrium thermodynamics. The colloidal flux is split up into an interfacial single-colloid contribution and a bulk contribution, followed by a determination of transport coefficients based on Onsager’s reciprocal relations. It is further shown how the phenomenological expression of the thermophoretic flux can be recovered when the fluid is at steady-state. The results issuing from this description are then discussed and compared to other existing approaches, some of which are shown to neglect the hydrodynamic character of colloidal thermophoresis. Chapter 3 is dedicated to the validation of the introduced theoretical framework by means of computer simulations, using a simulation technique known as multi-particle collision dynamics. More specifically, the dependence of the thermophoretic force on different system parameters is examined and deviations from the theoretical prediction are explained by an advective distortion of interfacial fluid properties at the colloidal surface. Chapter 4 presents steady-state measurements of functionalised colloids in a temperature gradient, showing how the addition of molecular surface groups increases the experimental complexity of thermophoretic motion. The relaxation process behind this steady-state is also studied, to determine how the relaxation speed depends on the applied temperature gradient. In chapter 5, a general conclusion is drawn from the presented work and its implications are briefly discussed in relation to the current state of knowledge. Finally, the discussion is closed with an outlook on remaining challenges in understanding colloidal motion that could be the subject of future research.

No description available.

Since their discovery in 1610 by Galileo Galilei, Saturn's rings continue to fascinate both experts and amateurs. Countless numbers of icy grains in almost Keplerian orbits reveal a wealth of structures such as ringlets, voids and gaps, wakes and waves, and many more. Grains are found to increase in size with increasing radial distance to Saturn. Recently discovered "propeller" structures in the Cassini spacecraft data, provide evidence for the existence of embedded moonlets. In the wake of these findings, the discussion resumes about origin and evolution of planetary rings, and growth processes in tidal environments. In this thesis, a contact model for binary adhesive, viscoelastic collisions is developed that accounts for agglomeration as well as restitution. Collisional outcomes are crucially determined by the impact speed and masses of the collision partners and yield a maximal impact velocity at which agglomeration still occurs. Based on the latter, a self-consistent kinetic concept is proposed. The model considers all possible collisional outcomes as there are coagulation, restitution, and fragmentation. Emphasizing the evolution of the mass spectrum and furthermore concentrating on coagulation alone, a coagulation equation, including a restricted sticking probability is derived. The otherwise phenomenological Smoluchowski equation is reproduced from basic principles and denotes a limit case to the derived coagulation equation. Qualitative and quantitative analysis of the relevance of adhesion to force-free granular gases and to those under the influence of Keplerian shear is investigated. Capture probability, agglomerate stability, and the mass spectrum evolution are investigated in the context of adhesive interactions. A size dependent radial limit distance from the central planet is obtained refining the Roche criterion. Furthermore, capture probability in the presence of adhesion is generally different compared to the case of pure gravitational capture. In contrast to a Smoluchowski-type evolution of the mass spectrum, numerical simulations of the obtained coagulation equation revealed, that a transition from smaller grains to larger bodies cannot occur via a collisional cascade alone. For parameters used in this study, effective growth ceases at an average size of centimeters. / Seit ihrer Entdeckung im Jahre 1610 durch Galileo Galilei faszinieren die Ringe des Saturn sowohl Laien als auch Experten. Planetare Ringe finden sich in der Äquatorialebene aller vier Riesenplaneten unseres Sonnensystems und sind eines der eindruckvollsten Beispiele granularer Gase. Darunter gehören die Saturnringe zu den Bekanntesten. Sie bergen eine Vielzahl von Strukturen und erstrecken sich über mehr als 240 000 Kilometer, wobei sie weit weniger als 100 Meter dick sind. Unzählige kleinerer Körper bewegen sich auf leicht exzentrischen Kepler-ähnlichen Bahnen um den Zentralplaneten und bestehen dabei vorwiegend aus Eis. Die seit Juli 2004 im Orbit um den Saturn befindliche Raumsonde Cassini liefert atemberaubende Bilder und Daten, die nicht nur neue Erkenntnisse liefern, sondern auch alte Fragestellungen neu aufleben lassen. Dazu gehört z.B. die Frage nach dem Ursprung und den Entwicklungsstufen planetarer Ringe. Kürzlich, im äusseren A-Ring entdeckte Kleinmonde, deren Existenz schon viel früher postuliert wurde, weisen auf eventuell stattfindende Wachstumsprozesse hin. Da sich planetare Ringe jedoch hauptsächlich innerhalb der sogenannten Roche-Zone des jeweiligen Planeten befinden, ist ein effektives, allein auf gravitativen Wechselwirkungen beruhendes Größenwachstum nicht zu erwarten. Der Einfluß von Teilchenadhäsion auf diese Prozesse ist bis dato fraglich. Im Rahmen dieser Dissertation ist ein Kontaktmodell für adhäsive, viskoelastische Binärstöße granularer Teilchen entwickelt worden, welches sowohl deren Agglomeration als auch Restitution gestattet. Chakateristisch für granulare Materie ist die dissipative Wechselwirkung der einzelnen Teilchen untereinander. Dieser Energieverlust wird gewöhnlich mittels des Restitutionskoeffizienten erfaßt, der das Verhältnis von Relativgeschwindigkeiten nach zu vor dem Stoß darstellt. Dieser Parameter ermöglicht es, Agglomeration und Restitution nicht nur qualitativ sondern auch quantitativ voneinander zu unterscheiden. Ferner ergibt sich eine maximale Impaktgeschwindigkeit, bei der eine Agglomeration noch immer möglich ist. Basierend auf der Existenz derartiger Grenzgeschwindigkeiten für Agglomeration und Fragmentation, wurde in dieser Dissertation ein selbstkonsistentes, kinetisches Strukturbildungsmodell vorgestellt und im Hinblick auf die Koagulation von Teilchen weitergehend untersucht. Eine Koagulationsgleichung, die einer eingeschränkten Haftwahrscheinlichkeit Rechnung trägt, ist analytisch hergeleitet worden. Aus ihr läßt sich die allgemein bekannte, aber ansonsten phenomenologische Smoluchowski Gleichung als ein Grenzfall ableiten, bei dem jeder mögliche Kontakt zur Koagulation führt. Qualitative und quantitative Untersuchungen der Relevanz von Adhäsion in kräftefreien und Kepler-gescherten Systemen beziehen sich auf die Stabilität von Zwei-Teilchen-Agglomeraten, die Wahrscheinlichkeit eines gegenseitigen "Einfangens" beider Teilchen, und die zeitliche Entwicklung der Größenverteilung unter Berücksichtigung der im ersten Teil dieser Arbeit eingeführten Kollisionsdynamik. Dabei ergab sich ein kritischer Abstand zum Zentralkörper, der das ansonsten in diesem Rahmen benutzte Roche Kriterium erweitert. Numerische Simulationen der vorgestellten Koagulationsgleichung zeigen deutlich, daß im Vergleich zu Smoluchowski-ähnlichem Verhalten, ein kollisionsbasiertes Wachstum von kleineren zu größeren Körpern nicht notwendigerweise auftritt. Lediglich Größen von Zentimetern konnten an dieser Stelle erreicht werden. Die Relevanz von adhäsiven Teilchenwechselwirkungen konnte damit nachgewiesen werden. Vermögen diese auch nicht für ein effektives Wachstum aufzukommen, so sind sie dennoch von Bedeutung für die kollektive Dynamik planetarer Ringe.

This thesis presents a joint experimental and theoretical study of a bimolecular collision between OH(A) and H₂ diatoms. The study focuses on the relationship between the initial, <b><i>j</i></b>, and final rotational angular momentum, <b><i>j'</i></b>. This relationship is explored from both a scalar point of view by measuring rotational energy transfer (RET), and a vectorial viewpoint by considering the collisional depolarisation. The experimental technique used in this investigation, Zeeman quantum beat spectroscopy, is first demonstrated by applying it to the determination of the lab-frame orientation of OH(X) photofragments following the photolysis of H₂O₂. The H₂O₂ is photolysed by circularly-polarised light at 248 nm, and Zeeman quantum beat spectroscopy probes the angular momentum orientation as a function of the photofragment spin-rotation level. The results of this experiment are compared with orientation parameters predicted by a simulation that couples the rotation of the parent molecule to the torsional motion during bond cleavage. The calculations from the model agree qualitatively with those from the experiment. The Zeeman quantum beat spectroscopy technique is then used to monitor the evolution of angular momentum polarisation of OH(A) radicals during collisions with H₂. The technique allows for the determination of depolarisation cross sections for oriented and aligned distributions, as a result of collisions with H₂. Alongside this, cross sections for collisional quenching to non-reactive OH(X)+H₂ and reactive H₂O+H products are determined. By resolving the fuorescence with a monochromator the contributions to depolarisation from elastic collisions (the elastic depolarisation cross sections) are measured alongside cross sections for RET. Cross sections for total depolarisation and rotational energy transfer demonstrate only weak dependence on the rotational quantum number of the OH(A) radical, <i>N</i>_OH. Competing quenching processes that fall with <i>N</i>_OH are likely a considerable cause of this weak dependence. Furthermore, the polarisation of the angular momentum of OH(A) is randomised following RET. The elastic depolarisation cross sections make only a small contribution to the depolarisation and fall with increasing <i>N</i>_OH. Collectively these trends have not been seen previously in similar studies on OH(A) collisions with atomic colliders. For the theoretical calculations, a four-atom quasi-classical trajectory (QCT) method has been developed, utilising Lagrangian multipliers to fix the OH(A) and H₂ bonds. The calculations demonstrate that collisions involving the formation of complexes that survive for several rotational periods are prevalent in this collision system, and that these lead to large amounts of depolarisation. The calculations also demonstrate that RET in the H₂ diatom supports higher levels of RET in OH(A) than seen in previous triatomic systems. Additionally, when one diatom is depolarised the accompanying diatom is typically also depolarised. These trends, at least in part, are owed to the highly attractive and anisotropic potential energy surface (PES) describing the interaction. The QCT calculations overestimate the experimentally-measured cross sections by more than a factor of 2. The calculations are adiabatic and do not account for the non-adiabatic activity associated with this collision system, and this is likely one cause of the discrepancies. In an attempt to further account for this overestimation, alternative angular momentum binning approaches for the QCT calculations are developed, but with limited success. Further exploration of the topology of the PES used in the calculations suggests that inadequacies in this surface are a major contributor to the discrepancies.