Graph neural networks (GNNs) have been shown to be extremely flexible and accurate in predicting the physical properties of molecules and crystals. However, traditional invariant GNNs are not compatible with directional properties, which currently limits their usage to the prediction of only invariant scalar properties. To address this issue, here we propose a general framework, i.e., an edge-based tensor prediction graph neural network, in which a tensor is expressed as the linear combination of the local spatial components projected on the edge directions of clusters with varying sizes. This tensor decomposition is rotationally equivariant and exactly satisfies the symmetry of the local structures. The accuracy and universality of our new framework are demonstrated by the successful prediction of various tensor properties from first to third order. The framework proposed in this work will enable GNNs to step into the broad field of prediction of directional properties.

Gas–particle interfaces are chemically active environments. This study investigates the reactivity of SO2 on NaCl surfaces using advanced experimental and theoretical methods with a NH4Cl substrate also examined for cation effects. Results show that NaCl surfaces rapidly convert to Na2SO4 with a new chlorine component when exposed to SO2 under low humidity. In contrast, NH4Cl surfaces have limited SO2 uptake and do not change significantly. Depth profiles reveal transformed layers and elemental ratios at the crystal surfaces. The chlorine species detected originates from Cl– expelled from the NaCl crystal structure, as determined by atomistic density functional theory calculations. Molecular dynamics simulations highlight the chemically active NaCl surface environment, driven by a strong interfacial electric field and the presence of sub-monolayer water coverage. These findings underscore the chemical activity of salt surfaces and the unexpected chemistry that arises from their interaction with interfacial water, even under very dry conditions.

Theoretical characterization of reactions of complex molecules depends on providing consistent accuracy for the relative energies of intermediates and transition states. Here we employ the DLPNO-CCSD(T) method with core–valence correlation, large basis sets, and extrapolation to the CBS limit to provide benchmark values for Diels–Alder transition states leading to competitive strained pentacyclic adducts. We then used those benchmarks to test a diverse set of wave function and density functional methods for the absolute and relative barrier heights of these transition states. Our results show that only a few of the tested density functionals can predict the absolute barrier heights satisfactorily, although relative barrier heights are more accurate. The most accurate functionals tested are ωB97M-V, M11plus, ωB97X-V, PBE-D3(0), M11, and MN15 with MUDs from best estimates less than 3.0 kcal. These findings can guide selection of density functionals for future studies of crowded, strained transition states of large molecules.

The relationship between matter properties and their atomic-scale structures is a challenging investigation. For relaxor ferroelectrics, correlating the relaxor mechanisms on the atomic scale to properties is still ambiguous. Here, the correlation between the atomic-scale structure and strain performance of 0.94 Bi0.5Na0.5TiO3-0.06BaTiO3 (94BNT-6BT) and 0.93 Bi0.5Na0.5TiO3-0.06BaTiO3-0.01BaZrO3 (93BNT-6BT-1BZ) is reported. The δTi–Bi/Na displacement vector map based on the annular dark field (ADF) scanning transmission electron microscopy (STEM) image demonstrates the coexistence of tetragonal (T) and rhombohedral (R) phases of the resulting ceramics, and BZ doping increases the proportion of the T phase. Furthermore, the enhanced annular bright field (eABF) STEM image demonstrates that BZ doped ceramics exhibit obvious oxygen octahedral tilt. The oxygen octahedral tilt increased gradually from the domain wall to the inner place of the nanodomain, indicating a regional consistency, which results in enhancement of the relaxor performance and stain property. This study opens exciting opportunities to the design of relaxor ferroelectrics with large strain for high-displacement actuator applications.

Generally, the 2D CsPbI3 layer capping on 3D counterparts has been considered as an effective strategy for both enhancing photovoltaic efficiency and stability. However, the intrinsically poor out-of-plane charge transport through the 2D layer remarkably hinders the overall performance of solar devices. To overcome such a challenge, we report the rationally designed 3D-CsPbI3/2D-(PYn)PbI4 (n = 1–4) heterojunctions with desirable energy level matching. It is evidenced that the valence band (VB) edge reconfiguration would occur with the increase of n, accompanied by the VB maximum (VBM) of the 2D component moving down from the higher level above that of the 3D component to the underneath. Consequently, the as-constructed 3D/2D-(PYn)PbI4 (n = 1, 2) heterojunctions exhibit optimal energy level matching, with accelerated transport of holes from 3D to 2D component and limited backflow of electrons. These findings might provide some meaningful insights on the energy level matching in 3D/2D perovskite heterojunctions.

The chaperonin GroEL is a multisubunit molecular machine that assists in protein folding in the Escherichia coli cytosol. Past studies have shown that GroEL undergoes large allosteric conformational changes during its reaction cycle. Here, we report single-molecule Förster resonance energy transfer measurements that directly probe the conformational transitions of one subunit within GroEL and its single-ring variant under equilibrium conditions. We find that four microstates span the conformational manifold of the protein and interconvert on the submillisecond time scale. A unique set of relative populations of these microstates, termed a macrostate, is obtained by varying solution conditions, e.g., adding different nucleotides or the cochaperone GroES. Strikingly, ATP titration studies demonstrate that the partition between the apo and ATP-ligated conformational macrostates traces a sigmoidal response with a Hill coefficient similar to that obtained in bulk experiments of ATP hydrolysis. These coinciding results from bulk measurements for an entire ring and single-molecule measurements for a single subunit provide new evidence for the concerted allosteric transition of all seven subunits.

Ion hydration in aqueous solutions plays a paramount role in many fields. Despite many studies on ion hydration, the nature of ion hydration is not consistently understood at the molecular level. Combining neutron scattering (NS), wide-angle X-ray scattering (WAXS), and molecular dynamics (MD), we quantify the ionic hydration degree (hydration ability) systematically for a series of alkali metal and halide ions based on static and dynamic hydration numbers. The former is based on the orientational correlation of water molecules bound to an ion derived from the positional information from NS and WAXS. The latter is defined as the mean number of water molecules remaining in the first coordination shell of an ion over a residence time of bound water molecules around the ion from MD. The static and dynamic hydration numbers distinguish hydration from coordination and quantify the ionic hydration degree, which provides a valuable reference for understanding various phenomena in nature.

The impact of mode-specific vibrational excitations on initial-preparation conditions was studied by examining the excited-state population decay rates in the nonadiabatic dynamics of methyl nitrate (CH3ONO2). In particular, exciting a few specific modes by adding a single quantum of energy clearly decelerated the nonadiabatic dynamics population decay rates. The underlying reason for this slower population decay was explained by analyzing the profiles of the excited-state potential energy surfaces in the Franck–Condon regions and the topology of the S1/S0 conical intersection. This study not only provides physical insights into the key mechanisms controlling nonadiabatic dynamics but also shows the possibility of controlling nonadiabatic dynamics via mode-specific vibrational excitations.

The quantum Drude oscillator (QDO) is an efficient yet accurate coarse-grained approach that has been widely used to model electronic and optical response properties of atoms and molecules as well as polarization and dispersion interactions between them. Three effective parameters (frequency, mass, and charge) fully characterize the QDO Hamiltonian and are adjusted to reproduce response properties. However, the soaring success of coupled QDOs for many-atom systems remains fundamentally unexplained, and the optimal mapping between atoms/molecules and oscillators has not been established. Here we present an optimized parametrization (OQDO) where the parameters are fixed by using only dipolar properties. For the periodic table of elements as well as small molecules, our model accurately reproduces atomic (spatial) polarization potentials and multipolar dispersion coefficients, elucidating the high promise of the presented model in the development of next-generation quantum-mechanical force fields for (bio)molecular simulations.

Traditional indirect flat-panel X-ray imaging (FPXI) uses inorganic scintillators with high-Z elements, which lack spectral information about X-ray photons and reflect only integrated X-ray intensity. To address this issue, we developed a stacked scintillator structure that combines organic and inorganic materials. This structure allows X-ray energies to be distinguished in a single shot by using a color or multispectral visible camera. However, the resolution of the resulting dual-energy image is primarily limited by the top scintillator layer. We inserted a layer of anodized aluminum oxide (AAO) between the double scintillators. This layer limits the lateral propagation of scintillation light, improves imaging resolution, and acts as a filter for X-rays. Our research demonstrates the advantages of stacked organic–inorganic scintillator structures for dual-energy X-ray imaging and provides novel and practical applications for relatively low-Z organic scintillators with high internal X-ray-to-light conversion efficiency.

It is highly challenging to achieve circularly polarized luminescence (CPL) switching by precisely tuning supramolecular interactions and unveiling the mechanism of supramolecular chirality inversion. Herein, we demonstrated CPL switching based on diethyl l-glutamate-9-cyanophenanthrene (LGCP) and diethyl l-glutamate-pyrene (LGP) via the precise regulation of supramolecular interactions. LGCP assembly driven by hydrogen bonding showed right CPL, while LGP assembly driven by π–π interaction led to left CPL. Remarkably, significant CPL switching was observed from the assemblies of LGCP/octafluoronaphthalene (OFN), attributed to the alteration of the dominating interaction from weak hydrogen bonding to rather strong π–π interaction, while the assemblies of LGP/OFN exhibited minimum CPL variation because the dominating π–π interaction within the assembly of LGP/OFN illustrated quite limited variations upon arene–perfluoroarene interaction. This work provides a feasible strategy toward the efficient modulation of the chiroptical properties of multiple component supramolecular systems, meanwhile offering possibilities for the mechanism exploration of the chirality inversion of supramolecular assemblies.

Heterogeneous photocatalytic systems are usually described based on electrochemistry, which the vast majority of interpretations and strategies for optimizing photocatalysts rely on. Charge carrier dynamics are usually in the spotlight, whereas the surface chemistry of the photocatalyst is neglected. This is unjustified, because studies on alcohol photoreforming on metal-decorated rutile single crystals revealed that the electrochemical reaction model is not generally applicable. Hence, many photocatalytic reactions may proceed in a different manner and the thermal chemistry needs to be accounted for. The new mechanism is particularly relevant for reactions in gaseous environments in the absence of solvated ionic species. Here, we compare both mechanisms and highlight their differences and consequences for photocatalysis. Based on alcohol photochemistry, we demonstrate the importance of thermal reactions in photocatalytic mechanisms and the relevance of systematic studies in different environments for a holistic understanding of photocatalysis.

Band gap tuning in mixed-halide perovskites enables efficient multijunction solar cells and LEDs. However, these wide band gap perovskites, which contain a mixture of iodide and bromide ions, are known to phase segregate under illumination, introducing voltage losses that limit stability. Previous studies have employed inorganic perovskites, halide alloys, and grain/interface passivation to minimize halide segregation, yet photostability can be further advanced. By focusing on the role of halide vacancies in anion migration, one expects to be able to erect local barriers to ion migration. To achieve this, we employ a 3D “hollow” perovskite structure, wherein a molecule that is otherwise too large for the perovskite lattice is incorporated. The amount of hollowing agent, ethane-1,2-diammonium dihydroiodide (EDA), varies the density of the hollow sites. Photoluminescence measurements reveal that 1% EDA in the perovskite bulk can stabilize a 40% bromine mixed-halide perovskite at 1 sun illumination intensity. These, along with capacitance–frequency measurements, suggest that hollow sites limit the mobility of the halide vacancies.

Organic materials can tune the optical properties in layered (2D) hybrid perovskites, although their impact on photophysics is often overlooked. Here, we use transient absorption spectroscopy to probe the Dion–Jacobson (DJ) and Ruddlesden–Popper (RP) 2D perovskite phases. We show the formation of charge transfer excitons in DJ phases, resulting in a photoinduced Stark effect which is shown to be dependent on the spacer size. By using electroabsorption spectroscopy, we quantify the strength of the photoinduced electric field, while temperature-dependent measurements demonstrate new features in the transient spectra of RP phases at low temperatures resulting from the quantum-confined Stark effect. This study reveals the impact of spacer size and perovskite phase configuration on charge transfer excitons in 2D perovskites of interest to their advanced material design.

Optical upconversion via a multiphoton absorption process converts incoherent low-energy photons to shorter wavelengths. In this contribution, we report a solid-state thin film for infrared-to-visible upconversion composed of plasmonic/TiO2 interfaces. When excited at λ = 800 nm, three photons are absorbed, leading to the excitation of TiO2 trap states into an emissive state in the visible domain. The plasmonic nanoparticle enhances the light absorption capabilities of the semiconductor, increasing emission efficiency by 20 times. We demonstrate that the plasmonic nanoparticle only changes the optical absorption of the semiconductor; i.e., the process is purely photonic. The process occurs in the ultrafast domain (<10 ps), contrasting with molecular triplet–triplet exciton annihilation, the commonly used method in photon upconversion, in the nano- to microsecond time scales. The process utilizes pre-existing trap states within the semiconductor bandgap and involves three-photon absorption.

A comprehensive study of vortex phases and vortex dynamics is presented for a recently discovered high-temperature superconductor YH6 with Tc(onset) of 215 K under a pressure of 200 GPa. The thermal activation energy (U0) is derived within the framework of the thermally activated flux flow (TAFF) theory. The activation energy yields a power law dependence U0 ∝ Hα on magnetic field with a possible crossover at a field around 8–10 T. Furthermore, we have depicted the vortex phase transition from the vortex-glass to vortex-liquid state according to the vortex-glass theory. Finally, vortex phase diagram is constructed for the first time for superhydrides. Very high estimated values of flux flow barriers U0(H) = (1.5–7) × 104 K together with high crossover fields make YH6 a rather outstanding superconductor as compared to most cuprates and iron-based systems. The Ginzburg number for YH6 Gi = (3–7) × 10–3 indicates that thermal fluctuations are not so strong and cannot broaden superconducting transitions in weak magnetic fields.

Cesium copper halides have the advantages of high photoluminescence quantum efficiency and good stability, making them attractive for replacing toxic lead halides in the field of perovskite light-emitting diodes (LEDs). However, due to their shallow conduction band and the lack of electron transport layers compatible with it, it remains a great challenge to achieve charge balance in LED devices. This drawback manifests as the accumulation of holes at the interface between the emitting layer and electron transport layer, resulting in nonradiative recombination. Here, we demonstrate an effective approach to address this issue by suppressing hole injection, which is realized through modification of the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) layer with polyethylenimine. This leads to cesium–copper–halide LEDs with a high external quantum efficiency of 5.6%, representing an advance in device architecture for efficient electroluminescence from cesium copper halides.

Direct nonoxidative coupling is a promising route for methane upgrading, yet its commercialization is hindered by the lack of efficient catalysts. Pt/CeO2 catalysts with isolated Pt species have attracted an increasing amount of interest in recent years. Herein, we studied the catalytic role and evolution of isolated Pt centers on CeO2 prepared by flame spray pyrolysis under the harsh reaction conditions of nonoxidative methane coupling. During the reaction at 800 °C, the isolated Pt sites sinter, leading to a loss of the ethylene and ethane yield. The agglomerated Pt can be redispersed by using an in situ regeneration strategy in oxygen. We found that isolated Pt centers are able to activate methane only at the initial reaction stage, and the CePt5 alloy acts as the active phase in the prolonged reaction.

The preparation of efficient and stable bifunctional electrocatalysts for electrochemical overall water splitting (OWS) to scale up commercial hydrogen production remains a great challenge. Here, we synthesized heterojunction structures consisting of Co9S8/Ni3S2 nanowire arrays and amorphous goethite (FeOOH, α-phase) particles as efficient OWS catalysts using an interface engineering strategy. The interfacial charge inhomogeneity caused by the heterojunction contact leads to the generation of a built-in electric field, which makes the electron-deficient FeOOH and electron-rich Co9S8/Ni3S2 favorable for hydrogen/oxygen evolution reaction, respectively, thus ensuring the excellent activity of FeOOH/Co9S8/Ni3S2 as a bifunctional catalyst. FeOOH/Co9S8/Ni3S2 exhibits impressive catalytic activity for the oxygen evolution reaction, achieving an ultralarge current density of 1000 mA cm–2 needed as low as 265 mV overpotential, and its stability was tested up to 1440 h. Furthermore, an excellent OWS output (1.55 V to generate 10 mA cm–2) is achieved by the bifunctional FeOOH/Co9S8/Ni3S2 catalysts.

The Tauc plot is widely used to determine the bandgap of semiconductors, but the actual plot often exhibits significant baseline absorption below the expected bandgap, leading to bandgap discrepancies from two different extrapolations. In this work, we first discuss the origin of baseline absorption and show that both extrapolation methods can produce significant errors by simulating Tauc plots with varying levels of baseline absorption. We then propose and experimentally verify a new method that idealizes the absorption spectrum by removing its baseline before constructing the Tauc plot. Finally, we apply this new method to cubic boron arsenide (c-BAs), resolve its bandgap discrepancies, and obtain a converging bandgap of 1.835 eV based on both previous and new transmission spectra. The method is applicable to both indirect and direct bandgap semiconductors with absorption spectrum measured via transmission or diffuse reflectance, which will become essential to obtain accurate values of their bandgaps.