Hydrogenation of C24_{24} carbon clusters : structural diversity and energetic properties

This work aims at exploring the potential energy surfaces of C$_{24}$H$_n${n=0,6,12,18,24} up to 20-25\,eV using the genetic algorithm in combination with the density functional based tight binding (DFTB) potential. The structural diversity of the non fragmented structures was analysed using order parameters which were chosen as the number of 5 or 6 carbon rings and the asphericity constant $\beta$. The most abundant and lowest energy population was found to correspond to a flakes population, constituted of isomers of variable shapes possessing a large number of 5 or 6-carbon rings. This population is characterized by a larger number of spherical isomers when $n_H/n_C$ increases. Simultaneously, the fraction of the pretzels population constituted of spherical isomers possessing fewer 5 or 6 carbon ring cycles increases. For all hydrogenation rates, the fraction of cages population remains extremely minor while the branched population is the highest energy population for all $n_H/n_C$ ratios. For all C$_{24}$H$_n${n=0,6,12,18,24} clusters, a detailed study of the evolution of the carbon ring size distribution as a function of energy clearly shows that the stability is correlated to the number of 6-carbon rings. A similar study for hybridization $sp^n$ (n=1-3) shows that the number of $sp^1$ carbon atoms increases with energy while globally the number of $sp^3$ carbon atoms increases with $n_H/n_C$. The average values of the ionization potentials of all populations were found to decrease when $n_H/n_C$ increases, ranging from 7.9\,eV down to 6.4\,eV that we correlated to carbon atoms hybridization $sp^n$ (n=1-3). These results are of astrophysical interest as they should be taken into account in astrophysical models especially regarding the role of carbonaceous species in the gas ionization.Comment: 37 pages, 13 figure

Spectroscopic investigation of interstellar hydrogenated carbon clusters. Infrared and optical spectra of C24Hn populations

International audienceContext. The assignment of the mid-infrared (mid-IR) emission features and plateaus observed in C-rich and H-rich regions of the interstellar medium (ISM) is still debated. Such mid-IR assignments must also be related to their contribution to the extinction curve in our galaxy and to the ultraviolet (UV) bump. Aims. The aim of this work is to investigate the influence of hydrogenation rate on the mid-IR spectra of populations of carbon clusters in order to constraint the nH /nC ratios in regions of the ISM where carbon is an important component. Their potential contribution to the extinction curve and in particular to the UV bump is also investigated. Methods. The absorption IR and optical spectra of tens of thousands of C24Hn (n=0,6,12,18,24) isomers classified into structural families-namely flakes, branched, pretzels, and cages-were computed using the density functional based tight binding electronic structure method and its time-dependent version, respectively. Final spectra were obtained by averaging the spectra of many individual isomers. Results. The shapes and the relative intensities of the bands centered at ∼ 3.25 and 3.40 µm and assigned to the C-H stretch of sp 2 and sp 3 carbon atoms, respectively, present a clear dependence on the nH /nC ratio. From a comparison with the astronomical spectrum from the Orion bar H2S1, the most interesting emitting candidates would pertain to the flakes population; this is the most energetically favorable family of clusters, possessing a high content of five and six carbon rings and being mostly planar, with no sp 1 carbon atoms and with a nH /nC ratio of lower than 0.5. The same conclusion is drawn when comparing the computed IR features in the [4-20 µm] region with the observed plateaus from some C-rich and H-rich planetary nebulae objects of the Small Magellanic Cloud. The contribution of the same family could be considered for the UV bump. When nH /nC increases, only a contribution to the high-energy part of the continuum due to σ → π excitations can reasonably be considered. Conclusions. These results bring some constraints on the structural features and on the nH /nC ratio of the hydrogenated carbon populations emitting in the mid-IR domain in interstellar objects such as protoplanetary and reflection nebulae. The flakes population, with a low nH /nC ratio, is an interesting candidate for the carbon population emitting in these regions, but not for that absorbing in the diffuse ISM. None of the populations studied in the present work can account for the UV bump, but they would contribute to a broad extinction rise in this domain. The computed features reported in this article could be used to interpret future astronomical data provided by the James Webb Space Telescope

Spectroscopie Infrarouge d'agrégats carbonés de chimie variée: une approche par échantillonage statistique

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Radiative relaxation in isolated large carbon clusters: Vibrational emission versus recurrent fluorescence

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Rare predicted loss-of-function variants of type I IFN immunity genes are associated with life-threatening COVID-19

BackgroundWe previously reported that impaired type I IFN activity, due to inborn errors of TLR3- and TLR7-dependent type I interferon (IFN) immunity or to autoantibodies against type I IFN, account for 15-20% of cases of life-threatening COVID-19 in unvaccinated patients. Therefore, the determinants of life-threatening COVID-19 remain to be identified in similar to 80% of cases.MethodsWe report here a genome-wide rare variant burden association analysis in 3269 unvaccinated patients with life-threatening COVID-19, and 1373 unvaccinated SARS-CoV-2-infected individuals without pneumonia. Among the 928 patients tested for autoantibodies against type I IFN, a quarter (234) were positive and were excluded.ResultsNo gene reached genome-wide significance. Under a recessive model, the most significant gene with at-risk variants was TLR7, with an OR of 27.68 (95%CI 1.5-528.7, P=1.1x10(-4)) for biochemically loss-of-function (bLOF) variants. We replicated the enrichment in rare predicted LOF (pLOF) variants at 13 influenza susceptibility loci involved in TLR3-dependent type I IFN immunity (OR=3.70[95%CI 1.3-8.2], P=2.1x10(-4)). This enrichment was further strengthened by (1) adding the recently reported TYK2 and TLR7 COVID-19 loci, particularly under a recessive model (OR=19.65[95%CI 2.1-2635.4], P=3.4x10(-3)), and (2) considering as pLOF branchpoint variants with potentially strong impacts on splicing among the 15 loci (OR=4.40[9%CI 2.3-8.4], P=7.7x10(-8)). Finally, the patients with pLOF/bLOF variants at these 15 loci were significantly younger (mean age [SD]=43.3 [20.3] years) than the other patients (56.0 [17.3] years; P=1.68x10(-5)).ConclusionsRare variants of TLR3- and TLR7-dependent type I IFN immunity genes can underlie life-threatening COVID-19, particularly with recessive inheritance, in patients under 60 years old