Nuclear spin conversion of water inside fullerene cages detected by low-temperature nuclear magnetic resonance

The water-endofullerene H2O@C60 provides a unique chemical system in which freely rotating water molecules are confined inside homogeneous and symmetrical carbon cages. The spin conversion between the ortho and para species of the endohedral H2O was studied in the solid phase by low-temperature nuclear magnetic resonance. The experimental data are consistent with a second-order kinetics, indicating a bimolecular spin conversion process. Numerical simulations suggest the simultaneous presence of a spin di↵usion process allowing neighbouring ortho and para molecules to exchange their angular momenta. Cross-polarization experiments found no evidence that the spin conversion of the endohedral H2O molecules is catalysed by 13C nuclei present in the cages

The dipolar endofullerene HF@C60

The cavity inside fullerenes provides a unique environment for the study of isolated atoms and molecules. We report encapsulation of hydrogen fluoride inside C60 using molecular surgery to give the endohedral fullerene HF@C60. The key synthetic step is the closure of the open fullerene cage while minimizing escape of HF. The encapsulated HF molecule moves freely inside the cage and exhibits quantization of its translational and rotational degrees of freedom, as revealed by inelastic neutron scattering and infrared spectroscopy. The rotational and vibrational constants of the encapsulated HF molecules were found to be redshifted relative to free HF. The NMR spectra display a large 1H-19F J coupling typical of an isolated species. The dipole moment of HF@C60 was estimated from the temperature-dependence of the dielectric constant at cryogenic temperatures and showed that the cage shields around 75% of the HF dipole

The Simons Observatory: Galactic Science Goals and Forecasts

Observing in six frequency bands from 27 to 280 GHz over a large sky area, the Simons Observatory (SO) is poised to address many questions in Galactic astrophysics in addition to its principal cosmological goals. In this work, we provide quantitative forecasts on astrophysical parameters of interest for a range of Galactic science cases. We find that SO can: constrain the frequency spectrum of polarized dust emission at a level of $\Delta\beta_d \lesssim 0.01$ and thus test models of dust composition that predict that $\beta_d$ in polarization differs from that measured in total intensity; measure the correlation coefficient between polarized dust and synchrotron emission with a factor of two greater precision than current constraints; exclude the non-existence of exo-Oort clouds at roughly 2.9$\sigma$ if the true fraction is similar to the detection rate of giant planets; map more than 850 molecular clouds with at least 50 independent polarization measurements at 1 pc resolution; detect or place upper limits on the polarization fractions of CO(2-1) emission and anomalous microwave emission at the 0.1% level in select regions; and measure the correlation coefficient between optical starlight polarization and microwave polarized dust emission in $1^\circ$ patches for all lines of sight with $N_{\rm H} \gtrsim 2\times10^{20}$ cm$^{-2}$. The goals and forecasts outlined here provide a roadmap for other microwave polarization experiments to expand their scientific scope via Milky Way astrophysics.Comment: Submitted to AAS journals. 33 pages, 10 figure

Planck intermediate results. LV. Reliability and thermal properties of high-frequency sources in the Second Planck Catalogue of Compact Sources

We describe an extension of the most recent version of the Planck Catalogue of Compact Sources (PCCS2), produced using a new multi-band Bayesian Extraction and Estimation Package (BeeP). BeeP assumes that the compact sources present in PCCS2 at 857 GHz have a dust-like spectral energy distribution (SED), which leads to emission at both lower and higher frequencies, and adjusts the parameters of the source and its SED to fit the emission observed in Planck's three highest frequency channels at 353, 545, and 857 GHz, as well as the IRIS map at 3000 GHz. In order to reduce confusion regarding diffuse cirrus emission, BeeP's data model includes a description of the background emission surrounding each source, and it adjusts the confidence in the source parameter extraction based on the statistical properties of the spatial distribution of the background emission. BeeP produces the following three new sets of parameters for each source: (a) fits to a modified blackbody (MBB) thermal emission model of the source; (b) SED-independent source flux densities at each frequency considered; and (c) fits to an MBB model of the background in which the source is embedded. BeeP also calculates, for each source, a reliability parameter, which takes into account confusion due to the surrounding cirrus. This parameter can be used to extract sub-samples of high-frequency sources with statistically well-understood properties. We define a high-reliability subset (BeeP/base), containing 26 083 sources (54.1% of the total PCCS2 catalogue), the majority of which have no information on reliability in the PCCS2. We describe the characteristics of this specific high-quality subset of PCCS2 and its validation against other data sets, specifically for: the sub-sample of PCCS2 located in low-cirrus areas; the Planck Catalogue of Galactic Cold Clumps; the Herschel GAMA15-field catalogue; and the temperature- and spectral-index-reconstructed dust maps obtained with Planck's Generalized Needlet Internal Linear Combination method. The results of the BeeP extension of PCCS2, which are made publicly available via the Planck Legacy Archive, will enable the study of the thermal properties of well-defined samples of compact Galactic and extragalactic dusty sources

Electrical detection of ortho-para conversion in fullerene-encapsulated water

Water exists in two spin isomers, ortho and para, that have different nuclear spin states. In bulk water, rapid proton exchange and hindered molecular rotation obscure the direct observation of two spin isomers. The supramolecular endofullerene H2O@C60 provides freely rotating, isolated water molecules even at cryogenic temperatures. Here we show that the bulk dielectric constant of this substance depends on the ortho/para ratio, and changes slowly in time after a sudden temperature jump, due to nuclear spin conversion. The attribution of the effect to ortho–para conversion is validated by comparison with nuclear magnetic resonance and quantum theory. The change in dielectric constant is consistent with an electric dipole moment of 0.51±0.05?Debye for an encapsulated water molecule, indicating the partial shielding of the water dipole by the encapsulating cage. The dependence of bulk dielectric constant on nuclear spin isomer composition appears to be a previously unreported physical phenomeno

Astroparticle Constraints from Cosmic Reionization and Primordial Galaxy Formation

We derived astroparticle constraints in different dark matter scenarios that are alternatives to cold dark matter (CDM): thermal relic warm dark matter, WDM; fuzzy dark matter, ψDM; self-interacting dark matter, SIDM; sterile neutrino dark matter, νDM. Our framework is based on updated determinations of the high-redshift UV luminosity functions for primordial galaxies to redshift z∼10, on redshift-dependent halo mass functions in the above DM scenarios from numerical simulations, and on robust constraints on the reionization history of the Universe from recent astrophysical and cosmological datasets. First, we built an empirical model of cosmic reionization characterized by two parameters, namely the escape fraction fesc of ionizing photons from primordial galaxies, and the limiting UV magnitude MUVlim down to which the extrapolated UV luminosity functions steeply increased. Second, we performed standard abundance matching of the UV luminosity function and the halo mass function, obtaining a relationship between UV luminosity and the halo mass, whose shape depends on an astroparticle quantity X specific to each DM scenario (e.g., WDM particle mass); we exploited such a relationship to introduce (in the analysis) a constraint from primordial galaxy formation, in terms of the threshold halo mass above which primordial galaxies can efficiently form stars. Third, we performed Bayesian inference on the three parameters fesc, MUVlim, and X via a standard MCMC technique, and compared the outcomes of different DM scenarios on the reionization history. We also investigated the robustness of our findings against educated variations of still uncertain astrophysical quantities. Finally, we highlight the relevance of our astroparticle estimates in predicting the behavior of the high-redshift UV luminosity function at faint, yet unexplored magnitudes, which may be tested with the advent of the James Webb Space Telescope

Synthesis and characterisation of an open-cage fullerene encapsulating hydrogen fluoride

The first encapsulation of hydrogen fluoride in an open-cage fullerene is reported. Solution and solid-state NMR spectra of the novel open-cage endofullerene are described

Emotion recognition and theory of mind weakness at school age in children born preterm

Social immaturity and impaired social functioning are topical issues in recent research in the field of prematurity. Social-cognitive skills and emotional processing, the neuropsychological correlates underlying social behavior, are key aspects of these issues