Iridium(I) and Iridium(III) Complexes Supported by a Diphenolate Imidazolyl-Carbene Ligand

Deprotonation of 1,3-di(2-hydroxy-5-tert-butylphenyl)imidazolium chloride (1a) followed by reaction with chloro-1,5-cyclooctadiene Ir(I) dimer affords the anionic Ir(I) complex [K][{OCO}Ir(cod)] (2: OCO = 1,3-di(2-hydroxy-5-tert-butylphenyl)imidazolyl; cod = 1,5-cyclooctadiene), the first Ir complex stabilized by a diphenolate imidazolyl-carbene ligand. In the solid state 2 exhibits square-planar geometry, with only one of the phenoxides bound to the metal center. Oxidation of 2 with 2 equiv of [FeCp_2][PF_6] generates the Ir(III) complex [{OCO}Ir(cod)(MeCN)][PF_6] (3). Reaction of 3 with H_2 results in the liberation of cyclooctane and a species capable of catalyzing the hydrogenation of cyclohexene to cyclohexane. Displacement of cyclooctadiene from 3 can be achieved by heating in acetonitrile to form [{OCO}Ir(MeCN)3][PF_6] (4) or by reaction with either PMe_3 or PCy_3 to generate [{OCO}Ir(PMe_3)_3][PF_6] (5) or [{OCO}Ir(PCy_3)_2(MeCN)][PF_6] (6), respectively. 6 reacts with CO in acetonitrile to give an equilibrium mixture of 6 and [{OCO}Ir(PCy_3)_2(CO)][PF_6] (7) and with chloride to generate [{OCO}Ir(PCy_3)_(2)Cl] (8). The solid-state structure of 8 shows that the diphenolate imidazolyl-carbene ligand is distorted from planarity; DFT calculations suggest this is due to an antibonding interaction between the phenolates and the metal center in the highest occupied molecular orbital (HOMO) of the complex. 8 undergoes two successive reversible one-electron oxidations in CH_(2)Cl_2 at −0.22 and at 0.58 V (vs ferrocene/ferrocenium); EPR spectra, mass spectroscopy, and DFT calculations suggest that the product of the first oxidation is [{OCO}Ir(PCy_3)_(2)Cl]+ (8+), with the unpaired electron occupying a molecular orbital that is delocalized over both the metal center and the diphenolate imidazolyl-carbene ligand

Dark Matter Constraints from the Sagittarius Dwarf and Tail System

2MASS has provided a three-dimensional map of the >360 degree, wrapped tidal tails of the Sagittarius (Sgr) dwarf spheroidal galaxy, as traced by M giant stars. With the inclusion of radial velocity data for stars along these tails, strong constraints exist for dynamical models of the Milky Way-Sgr interaction. N-body simulations of Sgr disruption with model parameters spanning a range of initial conditions (e.g., Sgr mass and orbit, Galactic rotation curve, halo flattening) are used to find parameterizations that match almost every extant observational constraint of the Sgr system. We discuss the implications of the Sgr data and models for the orbit, mass and M/L of the Sgr bound core as well as the strength, flattening, and lumpiness of the Milky Way potential.Comment: 6 pages, 0 figures. Contribution to proceedings of ``IAU Symposium 220: Dark Matter in Galaxies'', eds. S. Ryder, D.J. Pisano, M. Walker, and K. Freema

Papapetrou Energy-Momentum Tensor for Chern-Simons Modified Gravity

We construct a conserved, symmetric energy-momentum (pseudo-)tensor for Chern-Simons modified gravity, thus demonstrating that the theory is Lorentz invariant. The tensor is discussed in relation to other gravitational energy-momentum tensors and analyzed for the Schwarzschild, Reissner-Nordstrom, and FRW solutions. To our knowledge this is the first confirmation that the Reissner-Nordstrom and FRW metrics are solutions of the modified theory.Comment: 8 pages; typos corrected, references fixed, some calculations shortene

The growth of galaxies in cosmological simulations of structure formation

We use hydrodynamic simulations to examine how the baryonic components of galaxies are assembled, focusing on the relative importance of mergers and smooth accretion in the formation of ~L_* systems. In our primary simulation, which models a (50\hmpc)^3 comoving volume of a Lambda-dominated cold dark matter universe, the space density of objects at our (64-particle) baryon mass resolution threshold, M_c=5.4e10 M_sun, corresponds to that of observed galaxies with L~L_*/4. Galaxies above this threshold gain most of their mass by accretion rather than by mergers. At the redshift of peak mass growth, z~2, accretion dominates over merging by about 4:1. The mean accretion rate per galaxy declines from ~40 M_sun/yr at z=2 to ~10 M_sun/yr at z=0, while the merging rate peaks later (z~1) and declines more slowly, so by z=0 the ratio is about 2:1. We cannot distinguish truly smooth accretion from merging with objects below our mass resolution threshold, but extrapolating our measured mass spectrum of merging objects, dP/dM ~ M^a with a ~ -1, implies that sub-resolution mergers would add relatively little mass. The global star formation history in these simulations tracks the mass accretion rate rather than the merger rate. At low redshift, destruction of galaxies by mergers is approximately balanced by the growth of new systems, so the comoving space density of resolved galaxies stays nearly constant despite significant mass evolution at the galaxy-by-galaxy level. The predicted merger rate at z<~1 agrees with recent estimates from close pairs in the CFRS and CNOC2 redshift surveys.Comment: Submitted to ApJ, 35 pp including 15 fig

Competitive Oxidation and Protonation of Aqueous Monomethylplatinum(II) Complexes: A Comparison of Oxidants

[Pt^(II)(CH_3)Cl_3]^(2-) (1), generated at 95 °C in situ from Cs_2[Pt^(IV)(CH_3)_2Cl_4] in an aqueous solution of high chloride concentration and [H^+] = 0.2 M, undergoes competitive oxidation versus protonation (k_(ox)/k_(H+)) with several oxidants. A first-order dependence on oxidant concentration was determined for both CuCl_2 and FeCl_3 oxidations of 1, and k_(ox)/k_(H+) was determined to be 191 ± 24 and 14 ± 3. CuCl_2 was shown to catalyze the oxidation of 1 by dioxygen; however, [Pt^(II)Cl_4]^(2-) was also oxidized under these conditions. Anion 1, generated in a mixture of platinum(II) salts, [Cp_2Co^(III)]_2{[Pt^(II)Cl_4] + 1 + [Pt^(II)(CH_3)_2Cl_2] (4)}·xNaCl (5), also undergoes competitive oxidation and protonation at room temperature in D_2O when in the presence of oxidants. Increasing chloride decreases the ratio k_(ox)/k_(H+) for 1 when Na_2[Pt^(IV)Cl_6] is used as the oxidant, but when CuCl_2 is used as the oxidant, added chloride increases k_(ox)/k_(H+). The one-electron oxidants, Na_2[IrCl_6] and (NH_4)_2[Ce(NO_3)_6], were also shown to oxidize 1

Radiative Transitions in Charmonium from Lattice QCD

Radiative transitions between charmonium states offer an insight into the internal structure of heavy-quark bound states within QCD. We compute, for the first time within lattice QCD, the transition form-factors of various multipolarities between the lightest few charmonium states. In addition, we compute the experimentally unobservable, but physically interesting vector form-factors of the $\eta_c, J/\psi$ and $\chi_{c0}$. To this end we apply an ambitious combination of lattice techniques, computing three-point functions with heavy domain wall fermions on an anisotropic lattice within the quenched approximation. With an anisotropy $\xi=3$ at $a_s \sim 0.1 \mathrm{fm}$ we find a reasonable gross spectrum and a hyperfine splitting $\sim 90 \mathrm{MeV}$, which compares favourably with other improved actions. In general, after extrapolation of lattice data at non-zero $Q^2$ to the photopoint, our results agree within errors with all well measured experimental values. Furthermore, results are compared with the expectations of simple quark models where we find that many features are in agreement; beyond this we propose the possibility of constraining such models using our extracted values of physically unobservable quantities such as the $J/\psi$ quadrupole moment. We conclude that our methods are successful and propose to apply them to the problem of radiative transitions involving hybrid mesons, with the eventual goal of predicting hybrid meson photoproduction rates at the GlueX experiment.Comment: modified version as publishe

Universal Design for Instruction and Learning: A Pilot Study of Faculty Instructional Methods and Attitudes Related to Students with Disabilities in Higher Education

Universal design in the education setting is a framework of instruction that aims to be inclusive of different learners to reduce barriers for all students, including those with disabilities. We used the principles of Universal Design for Learning (UDL focuses on the learner) and Universal Design for Instruction (UDI focuses on instruction) as the basis for this study. The purposes of this study were to determine if faculty were incorporating UDI/UDL into their instruction, and their attitudes toward students with disabilities, as these could be barriers to learning. The study revealed that some faculty were incorporating principles of UDI/UDL into their instruction, the variety of methods used varied, and faculty attitudes still create barriers to an equitable educational environment for students with disabilities. More education and training is needed in working with students with disabilities and adapting teaching methods for these students using UDI/UDL

Hierarchical galaxy formation and substructure in the Galaxy's stellar halo

We develop an explicit model for the formation of the stellar halo from tidally disrupted, accreted dwarf satellites in the cold dark matter (CDM) framework, focusing on predictions testable with the Sloan Digital Sky Survey (SDSS) and other wide-field surveys. Subhalo accretion and orbital evolution are calculated using a semi-analytic approach within the Press-Schechter formalism. Motivated by our previous work, we assume that low-mass subhalos (v < 30 km/s) can form significant populations of stars only if they accreted a substantial fraction of their mass before the epoch of reionization. With this assumption, the model reproduces the observed velocity function of galactic satellites in the Local Group, solving the ``dwarf satellite problem'' without modifying the popular LCDM cosmology. The disrupted satellites yield a stellar distribution with a total mass and radial density profile consistent with those observed for the Milky Way stellar halo. Most significantly, the model predicts the presence of many large-scale, coherent substructures in the outer halo. These substructures are remnants of individual, tidally disrupted dwarf satellite galaxies. Substructure is more pronounced at large galactocentric radii because of the smaller number density of tidal streams and the longer orbital times. This model provides a natural explanation for the coherent structures in the outer stellar halo found in the SDSS commissioning data, and it predicts that many more such structures should be found as the survey covers more of the sky. The detection (or non-detection) and characterization of such structures could eventually test variants of the CDM scenario, especially those that aim to solve the dwarf satellite problem by enhancing satellite disruption.Comment: 12 pages, 8 figures, Submitted to Ap

Strong Outflows and Inefficient Star Formation in the Reionization-era Ultra-faint Dwarf Galaxy Eridanus II

We present novel constraints on the underlying galaxy formation physics (e.g., mass loading factor, star formation history, metal retention) at $z\gtrsim7$ for the low-mass ($M_*\sim10^5$ M$_\odot$) Local Group ultra-faint dwarf galaxy (UFD) Eridanus {\sc II} (Eri II). Using a hierarchical Bayesian framework, we apply a one-zone chemical evolution model to Eri II's CaHK-based photometric metallicity distribution function (MDF; [Fe/H]) and find that the evolution of Eri II is well-characterized by a short, exponentially declining star-formation history ($\tau_\text{SFH}=0.39\pm_{0.13}^{0.18}$ Gyr), a low star-formation efficiency ($\tau_\text{SFE}=27.56\pm_{12.92}^{25.14}$ Gyr), and a large mass-loading factor ($\eta=194.53\pm_{42.67}^{33.37}$). Our results are consistent with Eri II forming the majority of its stars before the end of reionization. The large mass-loading factor implies strong outflows in the early history of Eri II and is in good agreement with theoretical predictions for the mass-scaling of galactic winds. It also results in the ejection of $>$90\% of the metals produced in Eri II. We make predictions for the distribution of [Mg/Fe]-[Fe/H] in Eri II as well as the prevalence of ultra metal-poor stars, both of which can be tested by future chemical abundance measurements. Spectroscopic follow-up of the highest metallicity stars in Eri II ($\text{[Fe/H]} > -2$) will greatly improve model constraints. Our new framework can readily be applied to all UFDs throughout the Local Group, providing new insights into the underlying physics governing the evolution of the faintest galaxies in the reionization era.Comment: 20 pages; 12 figures, submitted to MNRA