Mechanical Stabilization of Helical Chirality in a Macrocyclic Oligothiophene

We introduce a design principle to stabilize helically chiral structures from an achiral tetrasubstituted [2.2]paracyclophane by integrating it into a macrocycle. The [2.2]paracyclophane introduces a three-dimensional perturbation into a nearly planar macrocyclic oligothiophene. The resulting helical structure is stabilized by two bulky substituents installed on the [2.2]paracyclophane unit. The increased enantiomerization barrier enabled the separation of both enantiomers. The synthesis of the target helical macrocycle 1 involves a sequence of halogenation and cross-coupling steps and a high-dilution strategy to close the macrocycle. Substituents tuning the energy of the enantiomerization process can be introduced in the last steps of the synthesis. The chiral target compound 1 was fully characterized by NMR spectroscopy and mass spectrometry. The absolute configurations of the isolated enantiomers were assigned by comparing the data of circular dichroism spectroscopy with TD-DFT calculations. The enantiomerization dynamics was studied by dynamic HPLC and variable-temperature 2D exchange spectroscopy and supported by quantum-chemical calculations

Large Conductance Variations in a Mechanosensitive Single-Molecule Junction

The appealing feature of molecular electronics is the possibility of exploiting functionality built within a single molecule. This functionality can be employed, for example, for sensing or switching purposes. Thus, ideally, the associated conductance changes should be sizable upon application of external stimuli. Here, we show that a molecular spring can be mechanically compressed or elongated to tune its conductance by up to an order of magnitude by controlling the quantum interference between electronic pathways. Oscillations in the conductance occur when the stress built up in the molecule is high enough to allow the anchoring groups to move along the surface in a stick-slip-like fashion. The mechanical control of quantum interference effects and the resulting large change in molecular conductance open the door for applications in, e.g., a minute mechanosensitive sensing device functional at room temperature.Comment: 23 pages, 6 figure

The Atacama Cosmology Telescope: Physical Properties and Purity of a Galaxy Cluster Sample Selected via the Sunyaev-Zel'dovich Effect

We present optical and X-ray properties for the first confirmed galaxy cluster sample selected by the Sunyaev-Zel'dovich Effect from 148 GHz maps over 455 square degrees of sky made with the Atacama Cosmology Telescope. These maps, coupled with multi-band imaging on 4-meter-class optical telescopes, have yielded a sample of 23 galaxy clusters with redshifts between 0.118 and 1.066. Of these 23 clusters, 10 are newly discovered. The selection of this sample is approximately mass limited and essentially independent of redshift. We provide optical positions, images, redshifts and X-ray fluxes and luminosities for the full sample, and X-ray temperatures of an important subset. The mass limit of the full sample is around 8e14 Msun, with a number distribution that peaks around a redshift of 0.4. For the 10 highest significance SZE-selected cluster candidates, all of which are optically confirmed, the mass threshold is 1e15 Msun and the redshift range is 0.167 to 1.066. Archival observations from Chandra, XMM-Newton, and ROSAT provide X-ray luminosities and temperatures that are broadly consistent with this mass threshold. Our optical follow-up procedure also allowed us to assess the purity of the ACT cluster sample. Eighty (one hundred) percent of the 148 GHz candidates with signal-to-noise ratios greater than 5.1 (5.7) are confirmed as massive clusters. The reported sample represents one of the largest SZE-selected sample of massive clusters over all redshifts within a cosmologically-significant survey volume, which will enable cosmological studies as well as future studies on the evolution, morphology, and stellar populations in the most massive clusters in the Universe.Comment: 20 pages, 15 figures, 6 tables. Accepted for publication in ApJ. Higher resolution figures available at: http://peumo.rutgers.edu/~felipe/e-prints

The Atacama Cosmology Telescope: Extragalactic Sources at 148 GHz in the 2008 Survey

We report on extragalactic sources detected in a 455 square-degree map of the southern sky made with data at a frequency of 148 GHz from the Atacama Cosmology Telescope 2008 observing season. We provide a catalog of 157 sources with flux densities spanning two orders of magnitude: from 15 to 1500 mJy. Comparison to other catalogs shows that 98% of the ACT detections correspond to sources detected at lower radio frequencies. Three of the sources appear to be associated with the brightest cluster galaxies of low redshift X-ray selected galaxy clusters. Estimates of the radio to mm-wave spectral indices and differential counts of the sources further bolster the hypothesis that they are nearly all radio sources, and that their emission is not dominated by re-emission from warm dust. In a bright (>50 mJy) 148 GHz-selected sample with complete cross-identifications from the Australia Telescope 20 GHz survey, we observe an average steepening of the spectra between 5, 20, and 148 GHz with median spectral indices of $\alpha_{\rm 5-20} = -0.07 \pm 0.06$, $\alpha_{\rm 20-148} = -0.39 \pm0.04$, and $\alpha_{\rm 5-148} = -0.20 \pm 0.03$. When the measured spectral indices are taken into account, the 148 GHz differential source counts are consistent with previous measurements at 30 GHz in the context of a source count model dominated by radio sources. Extrapolating with an appropriately rescaled model for the radio source counts, the Poisson contribution to the spatial power spectrum from synchrotron-dominated sources with flux density less than 20 mJy is C^{\rm Sync} = (2.8 \pm 0.3) \times 10^{-6} \micro\kelvin^2.Comment: Accepted to Ap

The Atacama Cosmology Telescope: A Measurement of the Cosmic Microwave Background Power Spectrum at 148 and 218 GHz from the 2008 Southern Survey

We present measurements of the cosmic microwave background (CMB) power spectrum made by the Atacama Cosmology Telescope at 148 GHz and 218 GHz, as well as the cross-frequency spectrum between the two channels. Our results clearly show the second through the seventh acoustic peaks in the CMB power spectrum. The measurements of these higher-order peaks provide an additional test of the {\Lambda}CDM cosmological model. At l > 3000, we detect power in excess of the primary anisotropy spectrum of the CMB. At lower multipoles 500 < l < 3000, we find evidence for gravitational lensing of the CMB in the power spectrum at the 2.8{\sigma} level. We also detect a low level of Galactic dust in our maps, which demonstrates that we can recover known faint, diffuse signals.Comment: 19 pages, 13 figures. Submitted to ApJ. This paper is a companion to Hajian et al. (2010) and Dunkley et al. (2010

Chemical profiles of the oxides on tantalum in state of the art superconducting circuits

Over the past decades, superconducting qubits have emerged as one of the leading hardware platforms for realizing a quantum processor. Consequently, researchers have made significant effort to understand the loss channels that limit the coherence times of superconducting qubits. A major source of loss has been attributed to two level systems that are present at the material interfaces. We recently showed that replacing the metal in the capacitor of a transmon with tantalum yields record relaxation and coherence times for superconducting qubits, motivating a detailed study of the tantalum surface. In this work, we study the chemical profile of the surface of tantalum films grown on c-plane sapphire using variable energy X-ray photoelectron spectroscopy (VEXPS). We identify the different oxidation states of tantalum that are present in the native oxide resulting from exposure to air, and we measure their distribution through the depth of the film. Furthermore, we show how the volume and depth distribution of these tantalum oxidation states can be altered by various chemical treatments. By correlating these measurements with detailed measurements of quantum devices, we can improve our understanding of the microscopic device losses

CLASS Angular Power Spectra and Map-Component Analysis for 40 GHz Observations through 2022

Measurement of the largest angular scale ($\ell < 30$) features of the cosmic microwave background (CMB) polarization is a powerful way to constrain the optical depth to reionization, $\tau$, and search for the signature of inflation through the detection of primordial $B$-modes. We present an analysis of maps covering nearly 75% of the sky made from the ground-based $40\,\mathrm{GHz}$ channel of the Cosmology Large Angular Scale Surveyor (CLASS) from August 2016 to May 2022. Using fast front-end polarization modulation from the Atacama Desert in Chile, we show this channel achieves higher sensitivity than the analogous frequencies from satellite measurements in the range $10 < \ell < 100$. After a final calibration adjustment, noise simulations show the CLASS linear (circular) polarization maps have a white noise level of $125 \,(130)\,\mathrm{\mu K\, arcmin}$. We measure the Galaxy-masked $EE$ and $BB$ spectra of diffuse synchrotron radiation and compare to space-based measurements at similar frequencies. In combination with external data, we expand measurements of the spatial variations of the synchrotron spectral energy density (SED) to include new regions of the sky and measure the faint diffuse SED in the harmonic domain. We place a new upper limit on a background of circular polarization in the range $5 < \ell < 125$ with the first bin showing $D_\ell < 0.023$ $\mathrm{\mu K^2_{CMB}}$ at 95% confidence. These results establish a new standard for recovery of the largest-scale CMB polarization from the ground and signal exciting possibilities when the higher sensitivity and higher frequency CLASS channels are included in the analysis.Comment: 36 pages, 24 figures, 6 tables. Submitted to The Astrophysical Journa

Venus Observations at 40 and 90 GHz with CLASS

Using the Cosmology Large Angular Scale Surveyor, we measure the disk-averaged absolute Venus brightness temperature to be 432.3 $\pm$ 2.8 K and 355.6 $\pm$ 1.3 K in the Q and W frequency bands centered at 38.8 and 93.7 GHz, respectively. At both frequency bands, these are the most precise measurements to date. Furthermore, we observe no phase dependence of the measured temperature in either band. Our measurements are consistent with a CO$_2$-dominant atmospheric model that includes trace amounts of additional absorbers like SO$_2$ and H$_2$SO$_4$.Comment: 7 pages, 3 figures, published in PS