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Abstract We present the first results of the holographic beam-mapping program for the Canadian Hydrogen Intensity Mapping Experiment (CHIME). We describe the implementation of a holographic technique as adapted for CHIME, and introduce the processing pipeline which prepares the raw holographic timestreams for analysis of beam features. We use data from six bright sources across the full 400–800 MHz observing band of CHIME to provide measurements of the copolar and cross-polar beam response in both amplitude and phase for all 1024 dual-polarized feeds in the array. In addition, we present comparisons with independent probes of the CHIME beam, which indicate the presence of polarized beam leakage. Holographic measurements of the beam have already been applied in science with CHIME, e.g., in estimating the detection significance of far-sidelobe fast radio bursts, and in validating the beam models used for CHIME’s first detections of 21 cm emission (in cross-correlation with measurements of large-scale structure from galaxy surveys and the Lyαforest). Measurements presented in this paper, and future holographic results, will provide a unique data set to characterize the CHIME beam and improve the experiment’s prospects for a detection of the baryon acoustic oscillation signal. 

We recently proposed a semi-stochastic approach to converging high-level coupled-cluster (CC) energetics, such as those obtained in the CC calculations with singles, doubles, and triples (CCSDT), in which the deterministic CC(P;Q) framework is merged with the stochastic configuration interaction Quantum Monte Carlo propagations [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017)]. In this work, we investigate the ability of the semi-stochastic CC(P;Q) methodology to recover the CCSDT energies of the lowest singlet and triplet states and the corresponding singlet–triplet gaps of biradical systems using methylene, (HFH)−, cyclobutadiene, cyclopentadienyl cation, and trimethylenemethane as examples. 

Abstract We report the detection of 21 cm emission at an average redshift $\overline{z}=2.3$in the cross-correlation of data from the Canadian Hydrogen Intensity Mapping Experiment (CHIME) with measurements of the Lyαforest from eBOSS. Data collected by CHIME over 88 days in the 400–500 MHz frequency band (1.8 <z< 2.5) are formed into maps of the sky and high-pass delay filtered to suppress the foreground power, corresponding to removing cosmological scales withk_∥≲ 0.13 Mpc⁻¹at the average redshift. Line-of-sight spectra to the eBOSS background quasar locations are extracted from the CHIME maps and combined with the Lyαforest flux transmission spectra to estimate the 21 cm–Lyαcross-correlation function. Fitting a simulation-derived template function to this measurement results in a 9σdetection significance. The coherent accumulation of the signal through cross-correlation is sufficient to enable a detection despite excess variance from foreground residuals ∼6–10 times brighter than the expected thermal noise level in the correlation function. These results are the highest-redshift measurement of 21 cm emission to date, and they set the stage for future 21 cm intensity mapping analyses atz> 1.8. 

In this work, a series of eight similarly structured perinone chromophores were synthesized and photophysically characterized to elucidate the electronic and structural tunability of their excited state properties, including excited state redox potentials and fluorescence lifetimes/quantum yields. Despite their similar structure, these chromophores exhibited a broad range of visible absorption properties, quantum yields, and excited state lifetimes. In conjunction with static and time-resolved spectroscopies from the ultrafast to nanosecond time regimes, time-dependent computational modeling was used to correlate this behavior to the relationship between non-radiative decay and the energy-gap law. Additionally, the ground and excited state redox potentials were calculated and found to be tunable over a range of 1 V depending on the diamine or anhydride used in their synthesis ( E red * = 0.45–1.55 V; E ox * = −0.88 to −1.67 V), which is difficult to achieve with typical photoredox-active transition metal complexes. These diverse chromophores can be easily prepared, and with their range of photophysical tunability, will be valuable for future use in photofunctional applications. 

J-dimer emission is an emergent property that occurs when pairs of ground state fluorophores associate, typically in a dilute solution medium. The resulting fluorescence is shifted with respect to the monomer. J-dimer emission, however, has never been observed in concentrated dispersions or in the solid state. We posited that multivariate (MTV) MOFs with double interwoven structures would help to isolate these dimers within their crystalline matrix. Using this strategy, J-aggregate density was controlled during crystallization by following a substitutional solid solution approach. Here, we identified the presence of J-dimers over the entire composition range for interwoven PIZOF-2 / NNU-28 structures with variable amounts of a diethynyl-anthracene aggregate-forming link. We produced bulk crystals that systematically shifted their fluorescence from green to red with lifetimes (up to 13 ns) and quantum yields (up to 76%) characteristic of π–π stacked aggregates. Photophysical studies also revealed an equilibrium constant of dimerization, K D = 1.5 ± 0.3 M −1 , enabling the first thermodynamic quantification of link–link interactions that occur during MOF assembly. Our findings elucidate the role that supramolecular effects play during crystallization of MTV MOFs, opening pathways for the preparation of solid-state materials with solution-like properties by design.