DFT-Assisted Design and Evaluation of Bifunctional Amine/Pyridine-Oxazoline Metal Catalysts for Additions of Ketones to Unactivated Alkenes and Alkynes

Bifunctional catalyst systems for the direct addition of ­ketones to unactivated alkenes/alkynes were designed and modeled by density functional theory (DFT). The designed catalysts possess bidentate ligands suitable for binding of pi-acidic group 10 metals capable of activating alkenes/alkynes, and a tethered organocatalyst amine to ­activate the ketone via formation of a nucleophilic enamine intermediate. The structures of the designed catalysts before and after C–C bond formation were optimized using DFT, and reaction steps involving group 10 metals were predicted to be significantly exergonic. A novel oxazoline precatalyst with a tethered amine separated by a meta-substituted benzene spacer was synthesized via a 10-step sequence that ­includes a key regioselective epoxide ring-opening step. It was combined with group 10 metal salts, including cationic Pd(II) and Pt(II), and screened for the direct addition of ketones to several alkenes and an ­internal alkyne. 1H NMR studies suggest that catalyst-catalyst inter­actions with this system via amine–metal coordination may preclude the desired addition reactions. The catalyst design approach disclosed here, and the promising calculations obtained with square planar group 10 metals, light a path for the discovery of novel bifunctional catalysts for C–C bond formation

The effect of intermediate mass close binaries on the chemical evolution of Globular Clusters

Context. The chemical processes during the Asymptotic Giant Branch (AGB) evolution of intermediate mass single stars predict most of the observations of the different populations in globular clusters although some important issues still need to be further clarified. In particular, to reproduce the observed anticorrelations of Na-O and Al-Mg, chemically enriched gas lost during the AGB phase of intermediate mass single stars must be mixed with matter with a pristine chemical composition. The source of this matter is still a matter of debate. Furthermore, observations reveal that a significant fraction of the intermediate mass and massive stars are born as components of close binaries. Aims. We will investigate the effects of binaries on the chemical evolution of Globular Clusters and on the origin of matter with a pristine chemical composition that is needed for the single star AGB scenario to work Methods. We use a population synthesis code that accounts for binary physics in order to estimate the amount and the composition of the matter returned to the interstellar medium of a population of binaries. Results. We demonstrate in the present paper that the mass lost by a significant population of intermediate mass close binaries in combination with the single star AGB pollution scenario may help to explain the chemical properties of the different populations of stars in Globular Clusters.Comment: 11 pages, 4 figures. Paper accepted for Astron. & Astrophy

350 Micron Observations of Ultraluminous Infrared Galaxies at Intermediate Redshifts

We present 350micron observations of 36 ultraluminous infrared galaxies (ULIRGs) at intermediate redshifts (0.089 <= z <= 0.926) using the Submillimeter High Angular Resolution Camera II (SHARC-II) on the Caltech Submillimeter Observatory (CSO). In total, 28 sources are detected at S/N >= 3, providing the first flux measurements longward of 100micron for a statistically significant sample of ULIRGs in the redshift range of 0.1 < z < 1.0. Combining our 350micron flux measurements with the existing IRAS 60 and 100micron data, we fit a single-temperature model to the spectral energy distribution (SED), and thereby estimate dust temperatures and far-IR luminosities. Assuming an emissivity index of beta = 1.5, we find a median dust temperature and far-IR luminosity of Td = 42.8+-7.1K and log(Lfir/Lsolar) = 12.2+-0.5, respectively. The far-IR/radio correlation observed in local star-forming galaxies is found to hold for ULIRGs in the redshift range 0.1 < z < 0.5, suggesting that the dust in these sources is predominantly heated by starbursts. We compare the far-IR luminosities and dust temperatures derived for dusty galaxy samples at low and high redshifts with our sample of ULIRGs at intermediate redshift. A general Lfir-Td relation is observed, albeit with significant scatter, due to differing selection effects and variations in dust mass and grain properties. The relatively high dust temperatures observed for our sample compared to that of high-z submillimeter-selected starbursts with similar far-IR luminosities suggest that the dominant star formation in ULIRGs at moderate redshifts takes place on smaller spatial scales than at higher redshifts.Comment: (24 pages in preprint format, 1 table, 7 figures, accepted for publication in ApJ

Delay time distribution of type Ia supernovae: theory vs. observation

Two formation scenarios are investigated for type Ia supernovae in elliptical galaxies: the single degenerate scenario (a white dwarf reaching the Chandrasekhar limit through accretion of matter transferred from its companion star in a binary) and the double degenerate scenario (the inspiraling and merging of two white dwarfs in a binary as a result of the emission of gravitational wave radiation). A population number synthesis code is used, which includes the latest physical results in binary evolution and allows to differentiate between certain physical scenarios (such as the description of common envelope evolution) and evolutionary parameters (such as the mass transfer efficiency during Roche lobe overflow). The thus obtained theoretical distributions of type Ia supernova delay times are compared to those that are observed, both in morphological shape and absolute number of events. The critical influence of certain parameters on these distributions is used to constrain their values. The single degenerate scenario alone is found to be unable in reproducing the morphological shape of the observational delay time distribution, while use of the double degenerate one (or a combination of both) does result in fair agreement. Most double degenerate type Ia supernovae are formed through a normal, quasi-conservative Roche lobe overflow followed by a common envelope phase, not through two successive common envelope phases as is often assumed. This may cast doubt on the determination of delay times by using analytical formalisms, as is sometimes done in other studies. The theoretical absolute number of events in old elliptical galaxies lies a factor of at least three below the rates that are observed. While this may simply be the result of observational uncertainties, a better treatment of the effects of rotation on stellar structure could mitigate the discrepancy.Comment: 5 pages, 4 figures, to appear in proceedings of "Binary Star Evolution: Mass Loss, Accretion, and Mergers

Quantum-Assisted Telescope Arrays

Quantum networks provide a platform for astronomical interferometers capable of imaging faint stellar objects. In a recent work [arXiv:1809.01659], we presented a protocol that circumvents transmission losses with efficient use of quantum resources and modest quantum memories. Here we analyze a number of extensions to that scheme. We show that it can be operated as a truly broadband interferometer and generalized to multiple sites in the array. We also analyze how imaging based on the quantum Fourier transform provides improved signal-to-noise ratio compared to classical processing. Finally, we discuss physical realizations including photon-detection-based quantum state transfer.Comment: 10 pages, 8 figures; v2 - clarifications and references; v3 - close to published versio

Advanced detectors and signal processing

Continued progress is reported toward development of a silicon on garnet technology which would allow fabrication of advanced detection and signal processing circuits on bubble memories. The first integrated detectors and propagation patterns have been designed and incorporated on a new mask set. In addition, annealing studies on spacer layers are performed. Based on those studies, a new double layer spacer is proposed which should reduce contamination of the silicon originating in the substrate. Finally, the magnetic sensitivity of uncontaminated detectors from the last lot of wafers is measured. The measured sensitivity is lower than anticipated but still higher than present magnetoresistive detectors

The Strategic Robustness of Mark-up Equilibria

This paper is an extension of the paper 'The Robustness of Agent-Based Models of Electricity Wholesale Markets', EPRG1213 which was motivated by the problem of analysing market power in liberalised electricity markets. That paper examined two particular forms of agent-based models commonly used in electricity market modelling, and showed that while these mark-up equilibria are robust against Nash deviations. This paper extends the earlier results to explain why these equilibria are robust to single firm Nash Cournot deviations but shows they are vulnerable to more sophisticated deviations

A 1200-micron MAMBO survey of ELAISN2 and the Lockman Hole - I. Maps, sources and number counts

The definitive version is available at www.blackwell-synergy.com '.--Copyright Blackwell Publishing. DOI : 10.1111/j.1365-2966.2004.08235.xWe present a deep, new 1200μm survey of the ELAISN2 and Lockman Hole fields using the Max Planck Millimeter Bolometer array (MAMBO). The areas surveyed are 160 arcmin2 in ELAISN2 and 197 arcmin2 in the Lockman Hole, covering the entire SCUBA ‘8mJy Survey’. In total, 27 (44) sources have been detected at a significance 4.0 ( 3.5 ). The primary goals of the survey were to investigate the reliability of (sub)millimetre galaxy (SMG) samples, to analyse SMGs using flux ratios sensitive to redshift at z > 3, and to search for ‘SCUBA drop-outs’, i.e. galaxies at z >> 3. We present the 1200μm number counts and find evidence of a fall at bright flux levels. Employing parametric models for the evolution of the local 60μm IRAS luminosity function (LF), we are able to account simultaneously for the 1200 and 850μm counts, suggesting that the MAMBO and SCUBA sources trace the same underlying population of high-redshift, dust-enshrouded galaxies. From a nearest-neighbour clustering analysis we find tentative evidence that themost significantMAMBO sources come in pairs, typically separated by 23′′. Our MAMBO observations unambiguously confirm around half of the SCUBA sources. In a robust sub-sample of 13 SMGs detected by both MAMBO and SCUBA at a significance 3.5 , only one has no radio counterpart. Furthermore, the distribution of 850/1200μmflux density ratios for this sub-sample is consistent with the spectroscopic redshift distribution of radio-detected SMGs (Chapman et al. 2003). Finally, we have searched for evidence of a high-redshift tail of SMGs amongst the 18 MAMBO sources which are not detected by SCUBA. While we cannot rule out that some of them are SCUBA drop-outs at z >> 3, their overall 850-to-1200μm flux distribution is statistically indistinguishable from that of the 13 SMGS which were robustly identified by both MAMBO and SCUBA.Peer reviewe

Wide-field mid-infrared and millimetre imaging of the high-redshift radio galaxy, 4C41.17

We present deep 350- and 1200-micron imaging of the region around 4C41.17 -- one of the most distant (z = 3.792) and luminous known radio galaxies -- obtained with the Submillimeter High Angular Resolution Camera (SHARC-II) and the Max Planck Millimeter Bolometer Array (MAMBO). The radio galaxy is robustly detected at 350- and 1200-micron, as are two nearby 850-micron-selected galaxies; a third 850-micron source is detected at 350-micron and coincides with a ~ 2-sigma feature in the 1200-micron map. Further away from the radio galaxy an additional nine sources are detected at 1200-micron, bringing the total number of detected (sub)millimeter selected galaxies (SMGs) in this field to 14. Using radio images from the Very Large Array (VLA) and Spitzer mid-infrared (mid-IR) data, we find statistically robust radio and/or 24-micron counterparts to eight of the 14 SMGs in the field around 4C41.17. Follow-up spectroscopy with Keck/LRIS has yielded redshifts for three of the eight robustly identified SMGs, placing them in the redshift range 0.5 < z < 2.7, i.e. well below that of 4C41.17. We infer photometric redshifts for a further four sources using their 1.6-micron (rest-frame) stellar feature as probed by the IRAC bands; only one of them is likely to be at the same redshift as 4C41.17. Thus at least four, and as many as seven, of the SMGs within the 4C41.17 field are physically unrelated to the radio galaxy. With the redshift information at hand we are able to constrain the observed over-densities of SMGs within radial bins stretching to R=50 and 100" (~ 0.4 and ~ 0.8Mpc at z ~ 3.8) from the radio galaxy to ~ 5x and ~ 2x that of the field, dropping off to the background value at R=150". [Abridged]Comment: 20 pages, 9 figures, accepted for publication in MNRA