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1. Large H 2 O solubility in dense silica and its implications for the interiors of water-rich planets

   https://doi.org/10.1073/pnas.1917448117  

   Nisr, Carole ; Chen, Huawei ; Leinenweber, Kurt ; Chizmeshya, Andrew ; Prakapenka, Vitali B. ; Prescher, Clemens ; Tkachev, Sergey N. ; Meng, Yue ; Liu, Zhenxian ; Shim, Sang-Heon ( April 2020 , Proceedings of the National Academy of Sciences)

   Sub-Neptunes are common among the discovered exoplanets. However, lack of knowledge on the state of matter in${\mathrm{H}}_2$O-rich setting at high pressures and temperatures ($P-T$) places important limitations on our understanding of this planet type. We have conducted experiments for reactions between${\mathrm{S}\mathrm{i}\mathrm{O}}_2$and${\mathrm{H}}_2$O as archetypal materials for rock and ice, respectively, at high$P-T$. We found anomalously expanded volumes of dense silica (up to 4%) recovered from hydrothermal synthesis above ∼24 GPa where the${\mathrm{C}\mathrm{a}\mathrm{C}\mathrm{l}}_2$-type (Ct) structure appears at lower pressures than in the anhydrous system. Infrared spectroscopy identified strong OH modes from the dense silica samples. Both previous experiments and our density functional theory calculations support up to 0.48 hydrogen atoms per formula unit of (${\mathrm{S}\mathrm{i}}_{1-x}{\mathrm{H}}_{4x}$)${\mathrm{O}}_2\hspace{0.17em}\left(x=0.12\right)$. At pressures above 60 GPa,${\mathrm{H}}_2$O further changes the structural behavior of silica, stabilizing a niccolite-type structure, which is unquenchable. From unit-cell volume and phase equilibrium considerations, we infer that the niccolite-type phase may contain H with an amount at least comparable with or higher than that of the Ct phase. Our results suggest that the phases containing both hydrogen and lithophile elements could be the dominant materials in the interiors of water-rich planets. Even for fully layered cases, the large mutual solubility could make the boundary between rock and ice layers fuzzy. Therefore, the physical properties of the new phases that we report here would be important for understanding dynamics, geochemical cycle, and dynamo generation in water-rich planets.

    

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2. The Ionization and Dynamics of the Makani Galactic Wind

   https://doi.org/10.3847/1538-4357/acbfae  

   Rupke, David S. ; Coil, Alison L. ; Perrotta, Serena ; Davis, Julie D. ; Diamond-Stanic, Aleksandar M. ; Geach, James E. ; Hickox, Ryan C. ; Moustakas, John ; Petter, Grayson C. ; Rudnick, Gregory H. ; et al ( April 2023 , The Astrophysical Journal)

   The Makani galaxy hosts the poster child of a galactic wind on scales of the circumgalactic medium. It consists of a two-episode wind in which the slow, outer wind originated 400 Myr ago (Episode I;R_I= 20 − 50 kpc) and the fast, inner wind is 7 Myr old (Episode II;R_II= 0 − 20 kpc). While this wind contains ionized, neutral, and molecular gas, the physical state and mass of the most extended phase—the warm, ionized gas—are unknown. Here we present Keck optical spectra of the Makani outflow. These allow us to detect hydrogen lines out tor= 30–40 kpc and thus constrain the mass, momentum, and energy in the wind. Many collisionally excited lines are detected throughout the wind, and their line ratios are consistent with 200–400 km s⁻¹shocks that power the ionized gas, withv_shock=σ_wind. Combining shock models, density-sensitive line ratios, and mass and velocity measurements, we estimate that the ionized mass and outflow rate in the Episode II wind could be as high as those of the molecular gas:$M_{\mathrm{II}}^{\mathrm{H}\mathrm{II}}\sim M_{\mathrm{II}}^{{\mathrm{H}}_2}=(1-2)\times {10}^9{M}_{\odot }$and$\mathit{dM}/{\mathit{dt}}_{\mathrm{II}}^{\mathrm{H}\mathrm{II}}\sim \mathit{dM}/{\mathit{dt}}_{\mathrm{II}}^{{\mathrm{H}}_2}=170-250M_{\odot }$yr⁻¹. The outer wind has slowed, so that$\mathit{dM}/{\mathit{dt}}_{\mathrm{I}}^{\mathrm{H}\mathrm{II}}\sim 10M_{\odot }$yr⁻¹, but it contains more ionized gas,$M_{\mathrm{I}}^{\mathrm{H}\mathrm{II}}=5\times {10}^9$M_⊙. The momentum and energy in the recent Episode II wind imply a momentum-driven flow (p“boost” ∼7) driven by the hot ejecta and radiation pressure from the Eddington-limited, compact starburst. Much of the energy and momentum in the older Episode I wind may reside in a hotter phase, or lie further into the circumgalactic medium.

    

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3. Aqueous reactions of organic triplet excited states with atmospheric alkenes

   https://doi.org/10.5194/acp-19-5021-2019  

   Kaur, Richie ; Hudson, Brandi M. ; Draper, Joseph ; Tantillo, Dean J. ; Anastasio, Cort ( January 2019 , Atmospheric Chemistry and Physics)

   Abstract. Triplet excited states of organic matter are formed when colored organicmatter (i.e., brown carbon) absorbs light. While these “triplets” can beimportant photooxidants in atmospheric drops and particles (e.g., theyrapidly oxidize phenols), very little is known about their reactivity towardmany classes of organic compounds in the atmosphere. Here we measure thebimolecular rate constants of the triplet excited state of benzophenone(³BP^∗), a model species, with 17 water-solubleC₃–C₆ alkenes that have either been found in theatmosphere or are reasonable surrogates for identified species. Measured rateconstants ($k_{\mathrm{ALK}+\mathrm{3}{\mathrm{BP}}^{\ast }}$) vary by a factor of 30 and are in therange of (0.24–7.5) ×10⁹ M⁻¹ s⁻¹. Biogenic alkenesfound in the atmosphere – e.g., cis-3-hexen-1-ol, cis-3-hexenyl acetate, andmethyl jasmonate – react rapidly, with rate constants above 1×10⁹ M⁻¹ s⁻¹. Rate constants depend on alkene characteristicssuch as the location of the double bond, stereochemistry, and alkylsubstitution on the double bond. There is a reasonable correlation between$k_{\mathrm{ALK}+\mathrm{3}{\mathrm{BP}}^{\ast }}$ and the calculated one-electron oxidation potential(OP) of the alkenes (R²=0.58); in contrast, rate constants are notcorrelated with bond dissociation enthalpies, bond dissociation freeenergies, or computed energy barriers for hydrogen abstraction. Using the OPrelationship, we estimate aqueous rate constants for a number of unsaturatedisoprene and limonene oxidation products with ³BP^∗: values are inthe range of (0.080–1.7) ×10⁹ M⁻¹ s⁻¹, withgenerally faster values for limonene products. Rate constants with lessreactive triplets, which are probably more environmentally relevant, arelikely roughly 25 times slower. Using our predicted rate constants, alongwith values for other reactions from the literature, we conclude thattriplets are probably minor oxidants for isoprene- and limonene-relatedcompounds in cloudy or foggy atmospheres, except in cases in which the tripletsare very reactive.

    

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4. Detection of Cosmological 21 cm Emission with the Canadian Hydrogen Intensity Mapping Experiment

   https://doi.org/10.3847/1538-4357/acb13f  

   The CHIME Collaboration ; Amiri, Mandana ; Bandura, Kevin ; Chen, Tianyue ; Deng, Meiling ; Dobbs, Matt ; Fandino, Mateus ; Foreman, Simon ; Halpern, Mark ; Hill, Alex S. ; et al ( April 2023 , The Astrophysical Journal)

   We present a detection of 21 cm emission from large-scale structure (LSS) between redshift 0.78 and 1.43 made with the Canadian Hydrogen Intensity Mapping Experiment. Radio observations acquired over 102 nights are used to construct maps that are foreground filtered and stacked on the angular and spectral locations of luminous red galaxies (LRGs), emission-line galaxies (ELGs), and quasars (QSOs) from the eBOSS clustering catalogs. We find decisive evidence for a detection when stacking on all three tracers of LSS, with the logarithm of the Bayes factor equal to 18.9 (LRG), 10.8 (ELG), and 56.3 (QSO). An alternative frequentist interpretation, based on the likelihood ratio test, yields a detection significance of 7.1σ(LRG), 5.7σ(ELG), and 11.1σ(QSO). These are the first 21 cm intensity mapping measurements made with an interferometer. We constrain the effective clustering amplitude of neutral hydrogen (Hi), defined as${\mathit{}}_{\mathrm{H}\mathrm{I}}\equiv {10}^3{\mathrm{\Omega }}_{\mathrm{H}\mathrm{I}}\left(b_{\mathrm{H}\mathrm{I}}+〈f{\mu }^2〉\right)$, where Ω_Hiis the cosmic abundance of Hi,b_Hiis the linear bias of Hi, and 〈fμ²〉 = 0.552 encodes the effect of redshift-space distortions at linear order. We find${\mathit{}}_{\mathrm{H}\mathrm{I}}={1.51}_{-0.97}^{+3.60}$for LRGs (z= 0.84),${\mathit{}}_{\mathrm{H}\mathrm{I}}={6.76}_{-3.79}^{+9.04}$for ELGs (z= 0.96), and${\mathit{}}_{\mathrm{H}\mathrm{I}}={1.68}_{-0.67}^{+1.10}$for QSOs (z= 1.20), with constraints limited by modeling uncertainties at nonlinear scales. We are also sensitive to bias in the spectroscopic redshifts of each tracer, and we find a nonzero bias Δv= − 66 ± 20 km s⁻¹for the QSOs. We split the QSO catalog into three redshift bins and have a decisive detection in each, with the upper bin atz= 1.30 producing the highest-redshift 21 cm intensity mapping measurement thus far.

    

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5. Analytic genericity of diffusing orbits in a priori unstable Hamiltonian systems

   https://doi.org/10.1088/1361-6544/ac50bb  

   Chen, Qinbo ; de la Llave, Rafael ( March 2022 , Nonlinearity)

   The genericity of Arnold diffusion in the analytic category is an open problem. In this paper, we study this problem in the followinga prioriunstable Hamiltonian system with a time-periodic perturbation${\mathcal{H}}_{\epsilon }(p,q,I,\phi ,t)=h(I)+\sum _{i=1}^n\pm \left(\frac{1}{2}{p}_i^2+V_i(q_i)\right)+\epsilon H_1(p,q,I,\phi ,t),$where$(p,q)\in {\mathbb{R}}^n\times {\mathbb{T}}^n$,$(I,\phi )\in {\mathbb{R}}^d\times {\mathbb{T}}^d$withn,d⩾ 1,V_iare Morse potentials, andɛis a small non-zero parameter. The unperturbed Hamiltonian is not necessarily convex, and the induced inner dynamics does not need to satisfy a twist condition. Using geometric methods we prove that Arnold diffusion occurs for generic analytic perturbationsH₁. Indeed, the set of admissibleH₁isC^ωdense andC³open (a fortiori,C^ωopen). Our perturbative technique for the genericity is valid in theC^ktopology for allk∈ [3, ∞) ∪ {∞,ω}.

    

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