The recent observation of stable quantized conductance in anatase TiO₂ resistive random access memory (ReRAM) devices opens up a new pathway toward the realization of brain-inspired neuromorphic computing devices. Herein, for the first time, ab initio calculations are implemented to understand the resistive switching phenomena in anatase TiO₂. Oxygen vacancy configurations with different charge states are studied to gain insight into the ON and OFF states of ReRAM devices. Among the trivacancy configurations, the V_o⁺ state is observed to induce highly dispersed defect states within the bandgap forming a charge density channel where the carriers behave as free electrons leading to the formation of a conducting filament (CF). On the contrary, the breakdown of the CF is noticed by the removal of an oxygen vacancy from the trivacancy configuration. In this OFF state, the defect state carriers are found to be highly localized. In addition, we have also investigated the effect of charge injection on the crystal field symmetry of the CF. The reduction of symmetry due to the trivacancy configuration lowers the e_g manifold energy, whereas the divacancy configuration lowers the t_2g manifold energy.

In the present work, the valence-bond-based compression approach for diabatization (VBCAD), previously presented in the literature [J. Phys. Chem. Lett. 2020, 11, 5295–5301] in the case of avoided crossings, is extended to the more general situation of conical intersections and their vicinity. A pointwise phase-correction scheme for diabatic states is proposed, based on the explicit use of the peculiarities of the nonorthogonality of ab initio valence bond (VB) theory. Rather than fitting or propagating nonadiabatic couplings, it allows us to determine the phase of diabatic states consistently and automatically at each geometry point. Moreover, it is shown that the undetermination of degenerate states around a conical intersection can be fixed naturally from a straightforward classical VB picture. These are illustrated with two prototypical symmetry-induced (Jahn–Teller) conical intersection models.

We study the vulnerability of single-molecule nanowires against a temporary disconnection of the junction. To this end, we compare the room and low-temperature junction formation trajectories along the opening and closing of gold–4,4′-bipyridine–gold single-molecule nanowires. In the low-temperature measurements, the cross-correlations between the opening and subsequent closing conductance traces demonstrate a strong structural memory effect: around half of the molecular opening traces exhibit similar, statistically dependent molecular features as the junction is closed again. This means that the junction stays rigid and the molecule remains protruding from one electrode even after the rupture of the junction, and therefore, the same single-molecule junction can be reestablished if the electrodes are closed again. In the room-temperature measurements, however, weak opening–closing correlations are found, indicating a significant rearrangement of the junction after the rupture and the related loss of structural memory effects.

Naturally occurring osmoprotectants are known to prevent aggregation of proteins under various stress factors including extreme pH and elevated temperature conditions. Here, we synthesized gold nanoparticles coated with selected osmolytes (proline, hydroxyproline, and glycine) and examined their effect on temperature-induced amyloid-formation of insulin hormone. These uniform, thermostable, and hemocompatible gold nanoparticles were capable of inhibiting both spontaneous and seed-induced amyloid aggregation of insulin. Both quenching and docking experiments suggest a direct interaction between the osmoprotectant-coated nanoparticles and aggregation-prone hydrophobic stretches of insulin. Circular-dichroism results confirmed the retention of insulin’s native structure in the presence of these nanoparticles. Unlike the indirect solvent-mediated effect of free osmolytes, the inhibition effect of osmolyte-coated gold nanoparticles was observed to be mediated through their direct interaction with insulin. The results signify the protection of the exposed aggregation-prone domains of insulin from temperature-induced self-assembly through osmoprotectant-coated nanoparticles, and such effect may inspire the development of osmolyte-based antiamyloid nanoformulations.

A series of organic host–guest materials with multifunctional luminescence were constructed. Four isoquinoline derivatives were used as the guests, and benzophenone was used as the host. The doped system exhibited excellent dual emission with cyan fluorescence and orange-yellow room-temperature phosphorescence, and the dual emission could be combined into almost pure white-light emission. Importantly, the relative intensity of the fluorescence–phosphorescence could be adjusted by changing the excitation wavelength, with the phosphorescence intensity being significantly higher than the fluorescence intensity under shorter excitation wavelengths and vice versa under longer excitation wavelengths. Therefore, three-color emission switching among cyan, white, and orange could be achieved by simply adjusting the excitation wavelength. The results of experimental and theoretical calculations indicated that the excitation-dependent emission colors were caused by different transfer paths for excitons under different excitation wavelengths. These materials with multifunctional luminescence could be used as writable inks for advanced anticounterfeiting.

As an effective method to improve the optical properties and stability of perovskite matrix, doped halide perovskites have attracted extensive attention in the field of optoelectronic applications. Herein, a series of all inorganic lead-free Te⁴⁺-doped Cs₂ZrCl₆ vacancy-ordered perovskites were successfully synthesized with different Te-doping concentrations by a solvothermal method, and deliberate Te⁴⁺-doping results in green-yellow triplet self-trapped exciton (STE) emission with a high photoluminescence quantum yield (PLQY) of 49.0%. The efficient energy transfer was observed from singlet to triplet emission. Further, the effects of A-site Rb alloying on the optical properties and stability were investigated. We found that A-site Rb alloying and C-site cohalogenation did not change the luminescence properties of Te⁴⁺, but the addition of a small amount of Rb⁺ can improve the PL intensity and moisture stability. Our results provide physical insights into the nS² Te⁴⁺-ion-doping-induced emissive mechanism and shed light on improving the environmental stability for further applications.

The nature of chemical bonding in actinide compounds (molecular complexes and materials) remains elusive in many respects. A thorough analysis of their electron charge distribution can prove decisive in elucidating bonding trends and oxidation states along the series. However, the accurate determination and robust analysis of the charge density of actinide compounds pose several challenges from both experimental and theoretical perspectives. Significant advances have recently been made on the experimental reconstruction and topological analysis of the charge density of actinide materials [Gianopoulos et al. IUCrJ, 2019, 6, 895]. Here, we discuss complementary advances on the theoretical side, which allow for the accurate determination of the charge density of actinide materials from quantum-mechanical simulations in the bulk. In particular, the extension of the Topond software implementing Bader’s quantum theory of atoms in molecules and crystals (QTAIMAC) to f- and g-type basis functions is introduced, which allows for an effective study of lanthanides and actinides in the bulk and in vacuo, on the same grounds. Chemical bonding of the tetraphenyl phosphate uranium hexafluoride cocrystal [PPh₄⁺][UF₆^–] is investigated, whose experimental charge density is available for comparison. Crystal packing effects on the charge density and chemical bonding are quantified and discussed. The methodology presented here allows reproducing all subtle features of the topology of the Laplacian of the experimental charge density. Such a remarkable qualitative and quantitative agreement represents a strong mutual validation of both approaches—experimental and computational—for charge density analysis of actinide compounds.

Near-infrared (NIR) thermally activated delayed fluorescence (TADF) materials have shown great application potential in organic light-emitting diodes, photovoltaics, sensors, and biomedicine. However, their fluorescence efficiency (Φ_F) is still highly inferior to those of conventional NIR fluorescent dyes, seriously hindering their applications. This study aims to provide theoretical guidance and experimental verification for highly efficient NIR-TADF molecular design. First, the light-emitting mechanism of two deep-red TADF molecules is revealed using first-principles calculation and the thermal vibration correlation function (TVCF) method. Then several acceptors are theoretically designed by changing the position of the cyano group or by introducing the phenanthroline into CNBPz, and 44 molecules are designed and studied theoretically. The photophysical properties of DA-3 in toluene and the amorphous state are simulated using a multiscale method combined with the TVCF method. The NIR-TADF property for DA-3 is predicted both in toluene and in the amorphous state. Experimental measurement further confirms that the TADF emission wavelength of DA-3 is 730 nm and Φ_F is as high as 20%. It is the highest fluorescence efficiency reported for TADF molecules with emission wavelengths larger than 700 nm in toluene. Our work provides an effective molecular design strategy, and a good candidate for highly efficient NIR-TADF emitters is also predicted.

Organic–inorganic hybrid metal halides with emissive organic cations are of great interest due to their structural diversity and interesting photophysical properties. Here, we assemble emissive organic cations (EnrofloH₂²⁺) with different metal–chloride anions (Pb₂Cl₆^2– to Bi₂Cl₁₀^4– to SnCl₆^2–) to form the new single crystal phases, and thus the photoluminescence properties of the metal halides, including Stokes shift, full width at half-maximum (FWHM), and photoluminescence quantum yield (PLQY) have been studied accordingly. (EnrofloH₂)SnCl₆·H₂O, as an example, possesses narrow FWHM and high PLQY, which are caused by the strong π–π stacking and inter- and intramolecular hydrogen bonds interactions. Compared with EnrofloH₂²⁺ cation in solution, the interactions generate a restraining effect and increase the rigid degree of EnrofloH₂²⁺ cation in the bulk single crystals. Our work clarifies the photophysical properties of the EnrofloH₂²⁺ organic cations by constructing the inter- and intramolecular interactions and boosts the further study of organic–inorganic hybrid metal halides materials with different luminescence mechanisms.

Two-dimensional (2D) Rashba semiconductors with structure inversion asymmetry and a spin–orbit coupling (SOC) effect show promising applications in nanospintronics, such as spin field effect transistors (FETs). Here, we systematically investigate the electronic structures and Rashba effect of 2D polar perovskites ABX₃ (A = Cs⁺ or Rb⁺; B = Pb²⁺ or Sn²⁺; X = Cl, Br, or I) by first-principles density functional theory calculations. We demonstrate that, except for the cubic case, 2D polar perovskites from tetragonal and orthorhombic three-dimensional (3D) bulks exhibit a strong intrinsic Rashba effect around the Γ point, due to their structure inversion asymmetry and the strong SOC effect of heavy atoms. In particular, 2D orthorhombic RbSnI₃ shows the largest Rashba constant of 1.176 eV Å among these polar perovskites, which is comparable to that of 3D bulk perovskites previously reported in experiments and theory. Furthermore, several 2D polar perovskites also show a strong electric field response. In particular, 2D tetragonal RbPbI₃ and tetragonal CsPbI₃ have strong electric field responses of >0.5 e Ų. Therefore, 2D polar perovskites as promising Rashba semiconductors possess large Rashba constants and strong electric field responses, resulting in a short spin channel length of tens of nanometers to preserve the spin coherence in spin FETs, superior to conventional 3D micrometer spin FETs.

Lipid-regulated oligomerization of membrane proteins plays a critical role in many cell-transduction pathways. However, molecular details of such processes are often hard to define experimentally. Here we reveal the key role of interfacial cardiolipin in regulating the functional dimerization of VsSemiSWEET (one of the smallest transporters) using molecular dynamics simulations. Four binding sites for cardiolipins are identified by calculating the spatiotemporal density distribution of cardiolipins and the free energy surface. Two types of dimerization modes (i.e., arm-to-body and body-to-body) are observed in the assembly process of VsSemiSWEET protomers. Binding of enough cardiolipin molecules at the dimer interface on the cytoplasmic side is found to be crucial in adjusting the monomer–dimer equilibrium and regulating the formation of functional dimers with proper conformation. Our results provide useful information on the relationship between lipid binding and functional dimerization of VsSemiSWEET and are helpful to understand the molecular mechanism of biological function of sugar transporters.

In situ X-ray scattering measurements of insect body surface lipids were successfully attempted by using a synchrotron X-ray source. The temperature-dependent structural changes of the cuticular hydrocarbons covering the forewing of an American cockroach were able to be followed, which showed that the majority of the hydrocarbons were in a liquid state even far below the critical temperature of water transpiration through the body surface. The results clearly demonstrated that synchrotron radiation X-ray scattering has the potential to obtain the detailed information about the intact lipid structure and physical properties on insect body surfaces.

Here a series of sp²–sp³ B_xN_x+1 (x = 1, 2, 3, 4, 5, 6) structures was constructed. These structures can be viewed as diamond-like BN blocks connected by single N–N bonds. Elastic constants and phonon dispersion curves confirm that all of the proposed structures are mechanically and dynamically stable. These structures all possess metallicity originating from the conductive channels formed by sp²-hybridized N atoms and adjacent sp³-hybridized B and N atoms. These structures exhibit tunable mechanical properties with a regular change in the sp²/sp³ ratio. The theoretical Vickers hardness increases and the ductility decreases as the number of diamond-like BN blocks increases, gradually approaching those of c-BN. Moreover, the convex hull at ambient pressure and 50 GPa indicates that high pressure is beneficial in the synthesis of these B–N phases. The simulated X-ray diffraction patterns of these structures were also calculated to provide more information for further experiments.

Zirconium nitride (ZrN) exhibits excellent mechanical and electronic properties and hosts a superconducting transition temperature (T_c) of 10.0 K that is on the high end among transition-metal nitrides. Here, we report on a first-principles study of tuning superconductivity of ZrN via strain engineering under extensive tensile and shear deformation modes. Our results reveal strikingly effective strain-induced enhancement of T_c up to 17.1 K, which is achieved under tensile strains along the high-symmetry crystallographic [001] deformation path. A systematic analysis of the calculated results indicates that such pronounced strain modulation of superconductivity stems from simultaneous increase of electronic density of states and softening of lattice vibration in the strain-deformed ZrN crystal. The present findings show that strain engineering offers an effective tool for optimizing superconductivity in transition-metal compounds, opening a fresh avenue for improving a major functionality of this class of materials that may find applications in advanced devices.

We investigate the orientation switching of individual azobenzene molecules adsorbed on a Au(111) surface using a laser-assisted scanning tunneling microscope (STM). It is found that the rotational motion of the molecule can be regulated by both sample bias and laser wavelength. By measuring the switching rate and state occupation as a function of both bias voltage and photon energy, the threshold in sample bias and the minimal photon energy are derived. It has been revealed that the tip-induced local electrostatic potential remarkably contributes to the reduction in hopping barrier. We also find that the tunneling electrons and photons play distinct roles in controlling rotational dynamics of single azobenzene molecules on the surface, which are useful for understanding dynamic behaviors in similar molecular systems.

Stacking two or more two-dimensional materials to form a heterostructure is becoming the most effective way to generate new functionalities for specific applications. Herein, using GW and Bethe–Salpeter equation simulations, we demonstrate the generation of linearly polarized, anisotropic intra- and interlayer excitonic bound states in the transition metal monochalcogenide (TMC) GeSe/SnS van der Waals heterostructure. The puckered structure of TMC results in the directional anisotropy in band structure and in the excitonic bound state. Upon the application of compressive/tensile biaxial strain dramatic variation (∓3%) in excitonic energies, the indirect-to-direct semiconductor transition and the red/blue shift of the optical absorption spectrum are observed. The variations in excitonic energies and optical band gap have been attributed to the change in effective dielectric constant and band dispersion upon the application of biaxial strain. The generation and control over the interlayer excitonic energies can find applications in optoelectronics and optical quantum computers and as a gain medium in lasers.

Direct X-ray detectors based on metal halide perovskites and their derivatives exhibit high sensitivity and low limit of detection (LoD). Compared with three-dimensional (3D) hybrid lead halide perovskites, low-dimensional A₃Bi₂I₉ perovskite derivatives (A = Cs, Rb, NH₄, CH₃NH₃(MA)) present better stability, greater environmental friendliness, and comparable X-ray detection performance. Here, we report FA₃Bi₂I₉ (FA= CH(NH₂)₂) single crystals (SCs) as a new member of the A₃Bi₂I₉ series for X-ray detection, which were prepared by the nucleation-controlled secondary solution constant temperature evaporation (SSCE) method. Centimeter-sized FA₃Bi₂I₉ SCs show a full width at half-maximum (fwhm) of 0.0096°, which is superior to that of recently reported Cs₃Bi₂I₉ (0.058°) and MA₃Bi₂I₉ SCs (0.024°) obtained by inverse temperature crystallization (ITC). The as-grown FA₃Bi₂I₉ SC shows a large resistivity of 7.8 × 10¹⁰ Ω cm and a high ion migration activation energy (E_a) of 0.56 eV, which can guarantee a low noise level and good operational stability under a large external bias. The FA₃Bi₂I₉ SC detector exhibits a LoD of 0.2 μGy_air s^–1, a sensitivity of 598.1 μC Gy_air ^–1 cm ^–2, and an X-ray detection efficiency of 33.5%, which are much better than those of the commercialized amorphous selenium detector. Results presented here will provide a new lead-free perovskite-type material to achieve green, sensitive, and stable X-ray detectors.

The structures of many membrane-bound proteins and polypeptides depend on the membrane potential. However, spectroscopically studying their structures under an applied field is challenging, because a potential is difficult to generate across more than a few bilayers. We study the voltage-dependent structures of the membrane-bound polypeptide, alamethicin, using a spectroelectrochemical cell coated with a rough, gold film to create surface plasmons. The plasmons sufficiently enhance the 2D IR signal to measure a single bilayer. The film is also thick enough to conduct current and thereby apply a potential. The 2D IR spectra resolve features from both 3₁₀- and α-helical structures and cross-peaks connecting the two. We observe changes in the peak intensity, not their frequencies, upon applying a voltage. A similar change occurs with pH, which is known to alter the angle of alamethicin relative to the surface normal. The spectra are modeled using a vibrational exciton Hamiltonian, and the voltage-dependent spectra are consistent with a change in angle of the 3₁₀- and α-helices in the membrane from 55 to 44°and from 31 to 60°, respectively. The 3₁₀- and α-helices are coupled by approximately 10 cm^–1. These experiments provide new structural information about alamethicin under a potential difference and demonstrate a technique that might be applied to voltage-gated membrane proteins and compared to molecular dynamics structures.

Using Mn-doped CsPbCl₃ nanocrystals (Mn:CsPbCl₃ NCs) to improve perovskite’s properties is becoming an important strategy. Here, we demonstrate a modified supersaturated recrystallization route to synthesize high-quality Mn:CsPbCl₃ NCs at room temperature. Unprecedentedly, sulfonate ligands with various concentrations are shown to successfully tune the dual-color emission of Mn:CsPbCl₃ NCs. Ultrafast transient absorption studies reveal that the host-to-dopant internal energy-transfer process involves the mediated traps. Interestingly, the dual-color emission is tuned via stabilizing mediated traps with a small amount of ligand (band edge (BE) emission reduces and Mn²⁺ emission increases), passivating the deep traps with a large amount of ligand (Mn²⁺ emission increases), and destroying Mn:CsPbCl₃ NCs with too much ligand (both BE and Mn²⁺ emission is quenched). Furthermore, the ligand tuning Mn²⁺ emission exhibits quenching for Cu²⁺ with high sensitivity and selectivity. Our work provides a new strategy to tune the optical properties of Mn:CsPbCl₃ NCs and presents its potential application in an optical detector.

The dynamic role of the conical intersection “seam” coordinate has been first revealed in the H fragmentation reaction of ortho(o)-cresol conformers. One of the (3N – 8) dimensional seam coordinates of the S₁(ππ*)/S₂(πσ*) conical intersection has been identified as the CH₃ torsional potential function. The tunneling dynamics of the reactive flux is dictated by its nuclear layout with respect to the CH₃ torsional angle, as the multidimensional tunneling barrier is dynamically shaped along the conical intersection seam. The effective tunneling-barrier weight-averaged over the quantum-mechanical probability along the CH₃ torsional angle perfectly explains the experimental finding: the sharp variation of the tunneling rate ((700–400) ps^–1) with the CH₃ torsional mode excitations within the narrow (0–100 cm^–1) energetic window. The much longer S₁ lifetime of cis compared to trans is ascribed to the higher-lying S₁/S₂ conical intersection of the former. With the use of distinct lifetimes, vibronic bands of each conformer could be completely separated.

The autodetachment dynamics of vibrational Feshbach resonances of the quadrupole-bound state (QBS) for the first time has been investigated in real time for the first excited state of the 4-cyanophenoxide (4-CP) anion. Individual vibrational resonances of the cryogenically cooled 4-CP QBS have been unambiguously identified, and their autodetachment rates state-specifically measured using the picosecond time-resolved pump–probe technique employing the photoelectron velocity-map imaging method. The autodetachment lifetime (τ) is found to be strongly dependent on mode, giving τ values of ∼56, ∼27, and ≤2.8 ps for the 12′¹ (E_vib = 406 cm^–1), 12′² (E_vib = 806 cm^–1), and 21′¹ (E_vib = 220 cm^–1) modes, respectively. The striking mode-specific behavior of the QBS lifetime has been invoked by the physical model in which the loosely bound electron falls off by the dynamic wobbling of the three-dimensional quadrupole moment ellipsoid associated with the corresponding vibrational motion in the autodetachment process.

Diffraction patterns observed in surface plasmon resonance imaging (SPRI) microscopy measurements of single gold nanorods (AuNRs) exhibit a complex behavior at wavelengths near the longitudinal plasmonic resonance band. SPRI microscopy measurements at 814 nm from AuNRs in three samples with resonance extinction maxima at 670, 816, and 980 nm reveal a variety of diffraction patterns with central peaks that are either positive, negative, or biphasic. A unitless ratio parameter M_R (−1 ≤ M_R ≤ 1) is created to describe the distribution of diffraction patterns. A purely negative (M_R = −1) central peak is observed for 30%, 57%, and 98% of the diffraction patterns in the 670, 816, and 980 nm samples, respectively. These results along with a theoretical modeling of the diffraction patterns with an anisotropic complex scattering coefficient suggests that this behavior only occurs for AuNRs when the laser wavelength used in SPRI experiments is shorter than the AuNR plasmonic resonance maxima, that is, in the anomalous dispersion region.

To understand night time airglow in the Meinel bands and heat conversion from the highly excited OH radicals in the upper atmosphere via the important atmospheric reaction H + O₃ → OH + O₂, we report here a quasi-classical trajectory study of the reaction dynamics on a recently developed full-dimensional potential energy surface (PES). Our results indicate that the reaction energy of this highly exoergic reaction is almost exclusively channeled into the vibration of the OH product, underscoring an extreme departure from the statistical limit. The calculated OH vibrational distribution is highly inverted and peaks near the highest accessible vibrational state, in excellent agreement with experimental observations, validating the accuracy of the PES. More importantly, the dynamical origin of the nonthermal excitation of the OH vibrational mode is identified by its large projection onto the reaction coordinate at a small potential barrier in the entrance channel, which controls the energy flow into various degrees of freedom in the products.

Living cells constantly remodel the shape of their lipid membranes. In the endoplasmic reticulum (ER), the reticulon homology domain (RHD) of the reticulophagy regulator 1 (RETR1/FAM134B) forms dense autophagic puncta that are associated with membrane removal by ER-phagy. In molecular dynamics (MD) simulations, we find that FAM134B-RHD spontaneously forms clusters, driven in part by curvature-mediated attractions. At a critical size, as in a nucleation process, the FAM134B-RHD clusters induce the formation of membrane buds. The kinetics of budding depends sensitively on protein concentration and bilayer asymmetry. Our MD simulations shed light on the role of FAM134B-RHD in ER-phagy and show that membrane asymmetry can be used to modulate the kinetic barrier for membrane remodeling.

Mechanistic understanding on the electronic structure of α′-Ga₂S₃ unravel that the electrons in nonbonding 3p_z orbitals of two-coordinated S^2– anions are photoexcited to the adjacent σ-type antibonding orbitals (Ga-4s and S-3p) and migrate thereafter to the surface along the a-axis. By introduction of the In–S antibonding on the one hand and modifying the local dipole moment on the other hand, the light absorption ability and charge separation efficiency can be both enhanced by In³⁺-to-Ga³⁺ substitution, and the photocatalytic H₂ evolution rate can be significantly promoted. Local geometric distortion is common in solid solutions, but its effect on charge migration behavior has yet been considered in semiconducting photocatalysis. Our case study on In³⁺-doped Ga₂S₃ is a good reminder of such the importance.

In the search for inhibitors of COVID-19, we have targeted the interaction between the human angiotensin-converting enzyme 2 (ACE2) receptor and the spike receptor binding domain (S1-RBD) of SARS-CoV-2. Virtual screening of a library of natural compounds identified Kobophenol A as a potential inhibitor. Kobophenol A was then found to block the interaction between the ACE2 receptor and S1-RBD in vitro with an IC₅₀ of 1.81 ± 0.04 μM and inhibit SARS-CoV-2 viral infection in cells with an EC₅₀ of 71.6 μM. Blind docking calculations identified two potential binding sites, and molecular dynamics simulations predicted binding free energies of −19.0 ± 4.3 and −24.9 ± 6.9 kcal/mol for Kobophenol A to the spike/ACE2 interface and the ACE2 hydrophobic pocket, respectively. In summary, Kobophenol A, identified through docking studies, is the first compound that inhibits SARS-CoV-2 binding to cells through blocking S1-RBD to the host ACE2 receptor and thus may serve as a good lead compound against COVID-19.

In on-surface chemistry, the efficient preparation of metal–organic hybrids is regarded as a primary path to mediate controlled synthesis of well-ordered low-dimensional organic nanostructures. The fundamental mechanisms in forming these hybrid structures, however, are so far insufficiently explored. Here, with scanning tunneling microscopy, we studied the bonding behavior of the adsorbed phenol derivatives with different molecular lengths. We reveal that shorter molecules favor bonding with extracted metal adatoms and result in metal–organic hybrids, whereas longer molecules prefer to bond with lattice metal atoms. The conclusions are further confirmed by density functional theory calculations.

The prevalence of ions at the aqueous interface has been widely recognized, but their effect on the structure of interfacial water (e.g., hydrogen (H)-bonding) remains enigmatic. Using heterodyne-detected vibrational sum frequency generation (HD-VSFG) and Raman difference spectroscopy with simultaneous curve fitting (DS-SCF) analysis, we show that the ion-induced perturbations of H-bonding at the air/water interface and in the bulk water are strongly correlated. Specifically, the structure-breaking anions such as ClO₃^– decrease the average H-bonding of water at the air/water interface, as it does to the water in its hydration shell in the bulk. The structure-making anion of the same series (IO₃^–) does exactly the reverse. None of the electrolytes (NaXO₃; X = Cl, Br, I) form well-defined electric double layers that significantly increase or reverse the hydrogen-down (H-down) orientation of water at the air/water interface. These results provide a unified picture of specific anion effect at the air/water interface and in the bulk water.

Probing bond breaking and making as well as related structural changes at the single-molecule level is of paramount importance for understanding the mechanism of chemical reactions. In this work, we report in situ tracking of bond breaking and making of an up-standing melamine molecule chemisorbed on Cu(100) by subnanometer resolved tip-enhanced Raman spectroscopy (TERS). We demonstrate a vertical detection depth of about 4 Å with spectral sensitivity at the single chemical-bond level, which allows us not only to justify the up-standing configuration involving a dehydrogenation process at the bottom upon chemisorption, but also to specify the breaking of top N–H bonds and the transformation to its tautomer during photon-induced hydrogen transfer reactions. Our results indicate the chemical and structural sensitivity of TERS for single-molecule recognition beyond flat-lying planar molecules, providing new opportunities for probing the microscopic mechanism of molecular adsorption and surface reactions at the chemical-bond level.

Herein, we employed lead-free Cs₃Cu₂I₅ perovskite films as the functional layers to construct Al/Cs₃Cu₂I₅/ITO memory devices and systematically investigated the impact on the corresponding resistive switching (RS) performance via adding different amounts of hydroiodic acid (HI) in Cs₃Cu₂I₅ precursor solution. The results demonstrated that the crystallinity and morphology of the Cs₃Cu₂I₅ films can be improved and the resistive switching performance can be modulated by adding an appropriate amount of HI. The obtained Cs₃Cu₂I₅ films by adding 5 μL HI exhibit the fewest lattice defects and flattest surface (RMS = 13.3 nm). Besides, the memory device, utilizing the optimized films, has a low electroforming voltage (1.44 V), a large on/off ratio (∼65), and a long retention time (10⁴ s). The RS performance impacted by adding HI, providing a scientific strategy for improving the RS performance of iodine halide perovskite-based memories.

We study nuclear quantum effects in H/D sticking to graphene, comparing scattering experiments at near-zero coverage with classical, quantized, and transition-state calculations. The experiment shows H/D sticking probabilities that are indistinguishable from one another and markedly smaller than those expected from a consideration of zero-point energy shifts of the chemisorption transition state. Inclusion of dynamical effects and vibrational anharmonicity via ring-polymer molecular dynamics (RPMD) yields results that are in good agreement with the experimental results. RPMD also reveals that nuclear quantum effects, while modest, arise primarily from carbon and not from H/D motion, confirming the importance of a C atom rehybridization mechanism associated with H/D sticking on graphene.

The typical layered transition metal dichalcogenide (TMDC) material, MoS₂, is considered a promising candidate for the next-generation electronic device due to its exceptional physical and chemical properties. In chemical vapor deposition synthesis, the sulfurization of MoO₃ powders is an essential reaction step in which the MoO₃ reactants are converted into MoS₂ products. Recent studies have suggested using an H₂S/H₂ mixture to reduce MoO₃ powders in an effective way. However, reaction mechanisms associated with the sulfurization of MoO₃ by the H₂S/H₂ mixture are yet to be fully understood. Here, we perform quantum molecular dynamics (QMD) simulations to investigate the sulfurization of MoO₃ flakes using two different gaseous environments: pure H₂S precursors and a H₂S/H₂ mixture. Our QMD results reveal that the H₂S/H₂ mixture could effectively reduce and sulfurize the MoO₃ reactants through additional reactions of H₂ and MoO₃, thereby providing valuable input for experimental synthesis of higher-quality TMDC materials.

The hydrogels of the polyelectrolytes polyethylenimine and poly(acrylic acid) are used to form a thin-layer interface on the gallium–indium eutectic alloy’s surface. The proposed method of gradually increasing the applied voltage reveals the possibility of formation of electronic components: diode, capacitor, resistor, and memristor. The components can be changed to each other many times. A multilayer perceptron model with one hidden layer and 12 nodes allows identifying hydrogels’ composition and automatically setting the desired architecture of electronic components. The design of electronic components makes it possible to easy-to-produce new electronic parts and programmable soft-matter electronics.

As organic photovoltaic performance approaches 20% efficiencies, causal structure–performance relationships must be established for devices to realize theoretical limits and become commercially competitive. Here, we reveal evidence of a causal relationship between mixed donor–acceptor interfaces and charge generation in polymer–fullerene solar cells. To do this, we combine a holistic loss analysis of device performance with quantitative synchrotron X-ray nanocharacterization to identify a >98% anticorrelation between field-dependent geminate recombination and nanodomain purity. Importantly, our analysis eliminates other possible explanations of the performance trends, a requirement to establish causality. The unprecedented granular level of our analysis also separates field-dependent and field-independent recombination at the interface, where we find for the first time that this system is free of field-independent recombination, a loss channel that plagues high-performance systems, including those with non-fullerene acceptors. This result broadens the case that minimizing mixed phases to promote sharp interfaces between pure aggregated domains is the ideal nanostructure for realizing theoretical efficiency limits of organic photovoltaics.

The fully inorganic perovskite lead cesium bromide single crystal (CsPbBr₃ SC) is considered as an excellent candidate semiconductor for photodetectors because of its superior humidity resistance, thermal stability, and light stability compared with organic–inorganic hybrid perovskites as well as its photoelectric properties such as large light absorption coefficient and ultralong carrier migration distance. In this Letter, we utilize the inverse temperature solubility of CsPbBr₃ in ternary solvents to grow large-sized CsPbBr₃ SCs. By the use of the (101) plane, CsPbBr₃ SC-based photodetectors are fabricated, which exhibit excellent polarized light response characteristics. The photocurrent relies on the polarization angle in a sinusoidal fashion and shows strong anisotropic optoelectronic properties. The photodetection performance perpendicular to the y axis is significantly higher than that parallel to the y axis, and the dichroic ratio under 405 nm illumination at a bias voltage of 1 V reaches 2.65. The experimental results are consistent with the results of first-principles calculations.

Current commercial lithium-ion battery (LIB) electrolytes are heavily influenced by the cost, chemical instability, and thermal decomposition of the lithium hexafluorophosphate salt (LiPF₆). This work studies the use of an unprecedently low Li salt concentration in a novel electrolyte, which shows equivalent capabilities to their commercial counterparts. Herein, the use of 0.1 M LiPF₆ in a ternary solvent mixture of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (TFE) (3EC/7EMC/20TFE, by weight) is investigated for the first time in LiNi_1/3Mn_1/3Co_1/3O₂ (NMC111)/graphite pouch cells. In solution, the Li⁺ transport number and diffusion are governed by the Grotthuss mechanism, with transport properties being independent of salt concentration. The proposed electrolyte operates in a wide temperature window (0–40 °C), is nonflammable (self-extinguishing under 2 s), and shows adequately fast wetting (4 s). When incorporated into the NMC/graphite pouch cell, it initially forms a solid electrolyte interphase (SEI) with minimal gas formation followed by a comparable battery performance to standard LiPF₆ electrolytes, validated by a high specific capacity of 165 mAh g^–1, Coulombic efficiencies of 99.3%, and capacity retention of 85% over 700 cycles.