Uranium(III) coordination chemistry and oxidation in a flexible small-cavity macrocycle

U(III) complexes of the conformationally flexible, small-cavity macrocycle trans-calix[2]benzene[2]pyrrolide (L)2–, [U(L)X] (X = O-2,6-tBu2C6H3, N(SiMe3)2), have been synthesized from [U(L)BH4] and structurally characterized. These complexes show binding of the U(III) center in the bis(arene) pocket of the macrocycle, which flexes to accommodate the increase in the steric bulk of X, resulting in long U–X bonds to the ancillary ligands. Oxidation to the cationic U(IV) complex [U(L)X][B(C6F5)4] (X = BH4) results in ligand rearrangement to bind the smaller, harder cation in the bis(pyrrolide) pocket, in a conformation that has not been previously observed for (L)2–, with X located between the two ligand arene rings

The impact of supercomputers on experimentation: A view from a national laboratory

The relative roles of large scale scientific computers and physical experiments in several science and engineering disciplines are discussed. Increasing dependence on computers is shown to be motivated both by the rapid growth in computer speed and memory, which permits accurate numerical simulation of complex physical phenomena, and by the rapid reduction in the cost of performing a calculation, which makes computation an increasingly attractive complement to experimentation. Computer speed and memory requirements are presented for selected areas of such disciplines as fluid dynamics, aerodynamics, aerothermodynamics, chemistry, atmospheric sciences, astronomy, and astrophysics, together with some examples of the complementary nature of computation and experiment. Finally, the impact of the emerging role of computers in the technical disciplines is discussed in terms of both the requirements for experimentation and the attainment of previously inaccessible information on physical processes

Low-lying bifurcations in cavity quantum electrodynamics

The interplay of quantum fluctuations with nonlinear dynamics is a central topic in the study of open quantum systems, connected to fundamental issues (such as decoherence and the quantum-classical transition) and practical applications (such as coherent information processing and the development of mesoscopic sensors/amplifiers). With this context in mind, we here present a computational study of some elementary bifurcations that occur in a driven and damped cavity quantum electrodynamics (cavity QED) model at low intracavity photon number. In particular, we utilize the single-atom cavity QED Master Equation and associated Stochastic Schrodinger Equations to characterize the equilibrium distribution and dynamical behavior of the quantized intracavity optical field in parameter regimes near points in the semiclassical (mean-field, Maxwell-Bloch) bifurcation set. Our numerical results show that the semiclassical limit sets are qualitatively preserved in the quantum stationary states, although quantum fluctuations apparently induce phase diffusion within periodic orbits and stochastic transitions between attractors. We restrict our attention to an experimentally realistic parameter regime.Comment: 13 pages, 10 figures, submitted to PR

Bs Mixing and Electric Dipole Moments in MFV

We analyze the general structure of four-fermion operators capable of introducing CP-violation preferentially in Bs mixing within the framework of Minimal Flavor Violation. The effect requires a minimum of O(Yu^4 Yd^4) Yukawa insertions, and at this order we find a total of six operators with different Lorentz, color, and flavor contractions that lead to enhanced Bs mixing. We then estimate the impact of these operators and of their close relatives on the possible sizes of electric dipole moments (EDMs) of neutrons and heavy atoms. We identify two broad classes of such operators: those that give EDMs in the limit of vanishing CKM angles, and those that require quark mixing for the existence of non-zero EDMs. The natural value for EDMs from the operators in the first category is up to an order of magnitude above the experimental upper bounds, while the second group predicts EDMs well below the current sensitivity level. Finally, we discuss plausible UV-completions for each type of operator.Comment: 11 pages; v2: references adde

Pesin's Formula for Random Dynamical Systems on RdR^d

Pesin's formula relates the entropy of a dynamical system with its positive Lyapunov exponents. It is well known, that this formula holds true for random dynamical systems on a compact Riemannian manifold with invariant probability measure which is absolutely continuous with respect to the Lebesgue measure. We will show that this formula remains true for random dynamical systems on $R^d$ which have an invariant probability measure absolutely continuous to the Lebesgue measure on $R^d$. Finally we will show that a broad class of stochastic flows on $R^d$ of a Kunita type satisfies Pesin's formula.Comment: 35 page

High momentum lepton pairs from jet-plasma interactions

We discuss the emission of high momentum lepton pairs (p_T>4 GeV) with low invariant masses (M << p_T) in central Au+Au collisions at RHIC (\sqrt{s_{NN}}=200 GeV). The spectra of dileptons produced through interactions of quark and antiquark jets with the quark-gluon plasma (QGP) have been calculated. Annihilation and Compton scattering processes, as well as processes benefitting from collinear enhancement, including Landau-Pomeranchuk-Migdal (LPM) effects, are calculated and convolved with a one dimensional hydrodynamic expansion. The jet-induced contributions are compared to thermal dilepton emission and Drell-Yan processes, and are found to dominate around p_T=4 GeV.Comment: Parallel talk given at QM2006, Shanghai November 2006. 4 pages, 3 figure

Chemical Equilibration in Hadronic Collisions

We study chemical equilibration in out-of-equilibrium Quark-Gluon Plasma using the first principles method of QCD effective kinetic theory, accurate at weak coupling. In longitudinally expanding systems--relevant for relativistic nuclear collisions--we find that for realistic couplings chemical equilibration takes place after hydrodynamization, but well before local thermalization. We estimate that hadronic collisions with final state multiplicities ${dN_\text{ch}}/{d\eta}\gtrsim 10^2$ live long enough to reach approximate chemical equilibrium, which is consistent with the saturation of strangeness enhancement observed in proton-proton, proton-nucleus and nucleus-nucleus collisions.Comment: 7 pages, 3 figures, see also our companion paper arXiv:1811.03068, v2 small changes, published versio

Self-diffusion of polymers in cartilage as studied by pulsed field gradient NMR

Pulsed field gradient (PFG) nuclear magnetic resonance (NMR) was used to investigate the self-diffusion behaviour of polymers in cartilage. Polyethylene glycol and dextran with different molecular weights and in different concentrations were used as model compounds to mimic the diffusion behaviour of metabolites of cartilage. The polymer self-diffusion depends extremely on the observation time: The short-time self-diffusion coefficients (diffusion time Delta approximately 15 ms) are subjected to a rather non-specific obstruction effect that depends mainly on the molecular weights of the applied polymers as well as on the water content of the cartilage. The observed self-diffusion coefficients decrease with increasing molecular weights of the polymers and with a decreasing water content of the cartilage. In contrast, the long-time self-diffusion coefficients of the polymers in cartilage (diffusion time Delta approximately 600 ms) reflect the structural properties of the tissue. Measurements at different water contents, different molecular weights of the polymers and varying observation times suggest that primarily the collagenous network of cartilage but also the entanglements of the polymer chains themselves are responsible for the observed restricted diffusion. Additionally, anomalous restricted diffusion was shown to occur already in concentrated polymer solutions

Anomalous exponents at the onset of an instability

Critical exponents are calculated exactly at the onset of an instability, using asymptotic expansiontechniques. When the unstable mode is subject to multiplicative noise whose spectrum at zero frequency vanishes, we show that the critical behavior can be anomalous, i.e. the mode amplitude X scales with departure from onset \mu as $~ \mu^\beta$ with an exponent $\beta$ different from its deterministic value. This behavior is observed in a direct numerical simulation of the dynamo instability and our results provide a possible explanation to recent experimental observations

A mathematical model for the capillary endothelial cell-extracellular matrix interactions in wound-healing angiogenesis

Angiogenesis, the process by which new blood capillaries grow into a tissue from surrounding parent vessels, is a key event in dermal wound healing, malignant-tumour growth, and other pathologic conditions. In wound healing, new capillaries deliver vital metabolites such as amino acids and oxygen to the cells in the wound which are involved in a complex sequence of repair processes. The key cellular constituents of these new capillaries are endothelial cells: their interactions with soluble biochemical and insoluble extracellular matrix (ECM) proteins have been well documented recently, although the biological mechanisms underlying wound-healing angiogenesis are incompletely understood. Considerable recent research, including some continuum mathematical models, have focused on the interactions between endothelial cells and soluble regulators (such as growth factors). In this work, a similar modelling framework is used to investigate the roles of the insoluble ECM substrate, of which collagen is the predominant macromolecular protein. Our model consists of a partial differential equation for the endothelial-cell density (as a function of position and time) coupled to an ordinary differential equation for the ECM density. The ECM is assumed to regulate cell movement (both random and directed) and proliferation, whereas the cells synthesize and degrade the ECM. Analysis and numerical solutions of these equations highlights the roles of these processes in wound-healing angiogenesis. A nonstandard approximation analysis yields insight into the travel ling-wave structure of the system. The model is extended to two spatial dimensions (parallel and perpendicular to the plane of the skin), for which numerical simulations are presented. The model predicts that ECM-mediated random motility and cell proliferation are key processes which drive angiogenesis and that the details of the functional dependence of these processes on the ECM density, together with the rate of ECM remodelling, determine the qualitative nature of the angiogenic response. These predictions are experimentally testable, and they may lead towards a greater understanding of the biological mechanisms involved in wound-healing angiogenesis