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1. Optical spectral weight, phase stiffness, and T _c bounds for trivial and topological flat band superconductors

   https://doi.org/10.1073/pnas.2106744118  

   Verma, Nishchhal ; Hazra, Tamaghna ; Randeria, Mohit ( August 2021 , Proceedings of the National Academy of Sciences)

   We present exact results that give insight into how interactions lead to transport and superconductivity in a flat band where the electrons have no kinetic energy. We obtain bounds for the optical spectral weight for flat-band superconductors that lead to upper bounds for the superfluid stiffness and the two-dimensional (2D)$T_c$. We focus on on-site attraction$\left|U\right|$on the Lieb lattice with trivial flat bands and on the π-flux model with topological flat bands. For trivial flat bands, the low-energy optical spectral weight${\tilde{D}}_{\text{low}}\le \tilde{n}\left|U\right|\mathrm{\Omega }/2$with$\tilde{n}=min\left(n,2-n\right)$, where n is the flat-band density and Ω is the Marzari–Vanderbilt spread of the Wannier functions (WFs). We also obtain a lower bound involving the quantum metric. For topological flat bands, with an obstruction to localized WFs respecting all symmetries, we again obtain an upper bound for${\tilde{D}}_{low}$linear in$\left|U\right|$. We discuss the insights obtained from our bounds by comparing them with mean-field and quantum Monte Carlo results.
2. (Nearly) Model-independent Constraints on the Neutral Hydrogen Fraction in the Intergalactic Medium at z ∼ 5–7 Using Dark Pixel Fractions in Lyα and Lyβ Forests

   https://doi.org/10.3847/1538-4357/aca678  

   Jin, Xiangyu ; Yang, Jinyi ; Fan, Xiaohui ; Wang, Feige ; Bañados, Eduardo ; Bian, Fuyan ; Davies, Frederick B. ; Eilers, Anna-Christina ; Farina, Emanuele Paolo ; Hennawi, Joseph F. ; et al ( January 2023 , The Astrophysical Journal)

   Cosmic reionization was the last major phase transition of hydrogen from neutral to highly ionized in the intergalactic medium (IGM). Current observations show that the IGM is significantly neutral atz> 7 and largely ionized byz∼ 5.5. However, most methods to measure the IGM neutral fraction are highly model dependent and are limited to when the volume-averaged neutral fraction of the IGM is either relatively low (${\overline{x}}_{\mathrm{H}\mathrm{I}}\lesssim {10}^{-3}$) or close to unity (${\overline{x}}_{\mathrm{H}\mathrm{I}}\sim 1$). In particular, the neutral fraction evolution of the IGM at the critical redshift range ofz= 6–7 is poorly constrained. We present new constraints on${\overline{x}}_{\mathrm{H}\mathrm{I}}$atz∼ 5.1–6.8 by analyzing deep optical spectra of 53 quasars at 5.73 <z< 7.09. We derive model-independent upper limits on the neutral hydrogen fraction based on the fraction of “dark” pixels identified in the Lyαand Lyβforests, without any assumptions on the IGM model or the intrinsic shape of the quasar continuum. They are the first model-independent constraints on the IGM neutral hydrogen fraction atz∼ 6.2–6.8 using quasar absorption measurements. Our results give upper limits ofmathvariant='normal'>HI(z=6.3)<0.79±0.04(1σ),${\overline{x}}_{\mathrm{H}\mathrm{I}}(z=6.5)<0.87\pm 0.03$(1σ), and${\overline{x}}_{\mathrm{H}\mathrm{I}}(z=6.7)<{0.94}_{-0.09}^{+0.06}$(1σ). The dark pixel fractions atz> 6.1 are consistent with the redshift evolution of the neutral fraction of the IGM derived from Planck 2018.

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3. Observation of chiral surface excitons in a topological insulator Bi ₂ Se ₃

   https://doi.org/10.1073/pnas.1813514116  

   Kung, H. -H. ; Goyal, A. P. ; Maslov, D. L. ; Wang, X. ; Lee, A. ; Kemper, A. F. ; Cheong, S. -W. ; Blumberg, G. ( February 2019 , Proceedings of the National Academy of Sciences)

   The protected electron states at the boundaries or on the surfaces of topological insulators (TIs) have been the subject of intense theoretical and experimental investigations. Such states are enforced by very strong spin–orbit interaction in solids composed of heavy elements. Here, we study the composite particles—chiral excitons—formed by the Coulomb attraction between electrons and holes residing on the surface of an archetypical 3D TI,${\mathrm{B}\mathrm{i}}_2{\mathrm{S}\mathrm{e}}_3$. Photoluminescence (PL) emission arising due to recombination of excitons in conventional semiconductors is usually unpolarized because of scattering by phonons and other degrees of freedom during exciton thermalization. On the contrary, we observe almost perfectly polarization-preserving PL emission from chiral excitons. We demonstrate that the chiral excitons can be optically oriented with circularly polarized light in a broad range of excitation energies, even when the latter deviate from the (apparent) optical band gap by hundreds of millielectronvolts, and that the orientation remains preserved even at room temperature. Based on the dependences of the PL spectra on the energy and polarization of incident photons, we propose that chiral excitons are made from massive holes and massless (Dirac) electrons, both with chiral spin textures enforced by strong spin–orbit coupling. A theoretical model basedmore »on this proposal describes quantitatively the experimental observations. The optical orientation of composite particles, the chiral excitons, emerges as a general result of strong spin–orbit coupling in a 2D electron system. Our findings can potentially expand applications of TIs in photonics and optoelectronics.

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4. Hydrogen bonding steers the product selectivity of electrocatalytic CO reduction

   https://doi.org/10.1073/pnas.1900761116  

   Li, Jingyi ; Li, Xiang ; Gunathunge, Charuni M. ; Waegele, Matthias M. ( April 2019 , Proceedings of the National Academy of Sciences)

   The product selectivity of many heterogeneous electrocatalytic processes is profoundly affected by the liquid side of the electrocatalytic interface. The electrocatalytic reduction of CO to hydrocarbons on Cu electrodes is a prototypical example of such a process. However, probing the interactions of surface-bound intermediates with their liquid reaction environment poses a formidable experimental challenge. As a result, the molecular origins of the dependence of the product selectivity on the characteristics of the electrolyte are still poorly understood. Herein, we examined the chemical and electrostatic interactions of surface-adsorbed CO with its liquid reaction environment. Using a series of quaternary alkyl ammonium cations (${\mathrm{m}\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$,${\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$,${\mathrm{p}\mathrm{r}\mathrm{o}\mathrm{p}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$, and${\mathrm{b}\mathrm{u}\mathrm{t}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$), we systematically tuned the properties of this environment. With differential electrochemical mass spectrometry (DEMS), we show that ethylene is produced in the presence of${\mathrm{m}\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$and${\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$cations, whereas this product is not synthesized in${\mathrm{p}\mathrm{r}\mathrm{o}\mathrm{p}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$- and${\mathrm{b}\mathrm{u}\mathrm{t}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$-containing electrolytes. Surface-enhanced infrared absorption spectroscopymore »(SEIRAS) reveals that the cations do not block CO adsorption sites and that the cation-dependent interfacial electric field is too small to account for the observed changes in selectivity. However, SEIRAS shows that an intermolecular interaction between surface-adsorbed CO and interfacial water is disrupted in the presence of the two larger cations. This observation suggests that this interaction promotes the hydrogenation of surface-bound CO to ethylene. Our study provides a critical molecular-level insight into how interactions of surface species with the liquid reaction environment control the selectivity of this complex electrocatalytic process.

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5. Intermediate valence state in YbB ₄ revealed by resonant x-ray emission spectroscopy

   https://doi.org/10.1088/1361-648X/ac7629  

   Frontini, Felix ; Lebert, Blair W. ; Cho, K. K. ; Song, M. S. ; Cho, B. K. ; Pollock, Christopher J. ; Kim, Young-June ( June 2022 , Journal of Physics: Condensed Matter)

   We report the temperature dependence of the Yb valence in the geometrically frustrated compound${\mathrm{Y}\mathrm{b}\mathrm{B}}_4$from 12 to 300 K using resonant x-ray emission spectroscopy at the Yb$L_{{\alpha }_1}$transition. We find that the Yb valence,v, is hybridized between thev = 2 andv = 3 valence states, increasing from$v=2.61\pm 0.01$at 12 K to$v=2.67\pm 0.01$at 300 K, confirming that${\mathrm{Y}\mathrm{b}\mathrm{B}}_4$is a Kondo system in the intermediate valence regime. This result indicates that the Kondo interaction in${\mathrm{Y}\mathrm{b}\mathrm{B}}_4$is substantial, and is likely to be the reason why${\mathrm{Y}\mathrm{b}\mathrm{B}}_4$does not order magnetically at low temperature, rather than this being an effect of geometric frustration. Furthermore, the zero-point valence of the system is extracted from our data and compared with other Kondo lattice systems. The zero-point valence seems to be weakly dependent on the Kondo temperature scale, but not on the valence change temperature scaleT_v.