Sub-Neptunes are the most common type of planet in our galaxy. Interior structure models suggest that the coldest sub-Neptunes could host liquid water oceans underneath their hydrogen envelopes—sometimes called “hycean” planets. JWST transmission spectra of the ∼250 K sub-Neptune K2-18 b were recently used to report detections of CH 4 and CO 2 , alongside weaker evidence of (CH 3 ) 2 S (dimethyl sulfide, or DMS). Atmospheric CO 2 was interpreted as evidence for a liquid water ocean, while DMS was highlighted as a potential biomarker. However, these notable claims were derived using a single data reduction and retrieval modeling framework, which did not allow for standard robustness tests. Here, we present a comprehensive reanalysis of K2-18 b’s JWST NIRISS SOSS and NIRSpec G395H transmission spectra, including the first analysis of the second-order NIRISS SOSS data. We incorporate multiple well-tested data reduction pipelines and retrieval codes, spanning 60 different data treatments and over 250 atmospheric retrievals. We confirm the detection of CH 4 (≈4 σ ), with a volume mixing ratio range , but we find no statistically significant or reliable evidence for CO 2 or DMS. Finally, we assess the retrieved atmospheric composition using photochemical-climate and interior models, demonstrating that our revised composition of K2-18 b can be explained by an oxygen-poor mini-Neptune without requiring a liquid water surface or life.
Anharmonicity strongly influences the absorption and emission spectra of polycyclic aromatic hydrocarbon (PAH) molecules. Here, IR–UV ion-dip spectroscopy experiments together with detailed anharmonic computations reveal the presence of fundamental, overtone, as well as 2- and 3-quanta combination band transitions in the far- and mid-infrared absorption spectra of phenylacetylene and its singly deuterated isotopologue. Strong absorption features in the 400–900 cm−1 range originate from CH(D) in-plane and out-of-plane wags and bends, as well as bending motions including the C≡C and CH bonds of the acetylene substituent and the aromatic ring. For phenylacetylene, every absorption feature is assigned either directly or indirectly to a single or multiple vibrational mode(s). The measured spectrum is dense, broad, and structureless in many regions but well characterized by computations. Upon deuteration, large isotopic shifts are observed. At frequencies above 1500 cm−1 for d1-phenylacetylene, a one-to-one match is seen when comparing computations and experiments with all features assigned to combination bands and overtones. The C≡C stretch observed in phenylacetylene is not observed in d1-phenylacetylene due to a computed 40-fold drop in intensity. Overall, a careful treatment of anharmonicity that includes 2- and 3-quanta modes is found to be crucial to understand the rich details of the infrared spectrum of phenylacetylene. Based on these results, it can be expected that such an all-inclusive anharmonic treatment will also be key for unraveling the infrared spectra of PAHs in general.
2 October 2019 in International Reviews in Physical Chemistry
Predicted almost forty years ago, the radiation from thermally populated excited electronic states has recently been recognised as an important cooling mechanism in free molecules and clusters. It has presently been observed from both inorganic clusters and carbon-based molecules in molecular beams and ion storage devices. Experiments have demonstrated that many of these systems radiate at rates approaching microsecond time scales, and often with a distinct dependence on the precise number of atoms in the system. The radiation acts as a strongly stabilising factor against both unimolecular decay and thermal electron emission. In astrophysical context, radiative cooling provides a mechanism to dissipate internal energy in star-forming processes, and stabilises molecules selectively in the circumstellar medium. The consequences of an active radiative cooling channel for nanoparticle production will likewise favour special sizes in non-equilibrium formation processes. In this review, the radiative cooling of clusters is presented and illustrated with examples of experiments performed on small carbon, metal, and semiconductor clusters, and on PAH molecules. The experimental and theoretical techniques used are discussed, together with the consequences of radiative cooling on size-to-size stability patterns of clusters.
Far-infrared multiple photon dissociation spectroscopy is used in combination with density functional theory calculations to determine the structures of isolated Au n+ ( n ≤ 9) clusters.