Lithium metal anodes offer unmatched theoretical capacity amongst candidate battery materials, yet their commercial viability remains limited by uncontrolled dendrite growth and solid electrolyte interphase (SEI) formation. Whilst recent work has established that applied voltage controls lithium morphology through potential-dependent surface tension, how voltage determines which electrolyte decomposition products preferentially bind to those evolving surfaces remains unexplored. Here, we employ grand canonical density functional theory with implicit solvation to systematically examine how F-, O2-, and CO32- compete for binding sites across thirteen crystallographic orientations spanning an electrochemically relevant potential window (-1.75 to +1.0 V vs. Li/Li+). Our calculations reveal systematic morphological transitions with decreasing potential: {311} dominates exclusively at +1.0 V, {320} emerges at intermediate potentials, and {110} progressively increases from 30% at -1.0 V to complete dominance at -1.75 V, yielding a rhombic dodecahedron consistent with ultrafast electrodeposition experiments. Competitive adsorption on the thermodynamically dominant surface at each voltage establishes a clear hierarchy: carbonate binding exceeds fluoride by 1.75-2.42 eV throughout the reducing potentials relevant to lithium deposition (-0.5 to -1.75 V), whilst fluoride achieves thermodynamic preference only under oxidising conditions (+1.0 V on {311}). The coupling between morphology and chemistry emerges through surface-dependent site availability-{110} and {311} present 3-fold hollow sites whilst {320} offers 4-fold configurations-which alters binding geometries as voltage drives morphological transitions. These findings rationalise the ubiquitous presence of Li2CO3 in experimental SEI characterisation and suggest that achieving LiF-rich interfaces requires kinetic strategies that bypass thermodynamic equilibrium. Our results establish that applied voltage functions as a thermodynamic selector, simultaneously shaping both the structure and composition of the lithium-electrolyte interface.

Combining optical and magnetic functionalities into memristors is an attractive option to expand applications into image recognition, information storage, and low power processing. Here, we have fabricated ferromagnetic-fullerene-manganese oxide structures that display a hysteretic, nonlinear I-V characteristic and a photovoltaic effect with a photocurrent dependent on the relative alignment of the magnetization and the light polarization vector. Reversible, voltage-induced oxygen migration from manganese oxide into the molecular layer reduces the resistivity of the device by several orders of magnitude, eliminates the nonlinear transport, and quenches the photovoltaic response, giving rise to an optically sensitive memristor where the photocurrent is dependent on both the electrical and magnetic history of the device. Density functional theory calculations attribute the origin of these effects to changes in the electronic structure at the Fermi level and a reduction of the interface dipole upon ionic migration. These results open research pathways towards single-molecule scale memristive memories with optical excitation, electrical readout and magnetic sensing functionalities.

Performing density functional theory (DFT) calculations requires a careful choice of computational parameters to ensure convergence and obtain meaningful results. This represents a particularly important problem for high-throughput and agentic workflows, where due to computational cost, any additional convergence studies are preferably avoided. So, there is a need for tools and models which are able to predict DFT parameters from basic input information, such as a structure. In this work, we develop a machine learning approach to predict the appropriate k-point sampling in DFT calculations and generate the input files for Quantum Espresso self-consistent field calculations. To achieve this, we first generated a training dataset comprising over 20 000 materials, each with an energy convergence threshold of 1 meV per atom. Several ML models were evaluated for their ability to predict k-point distance, and uncertainty estimation was incorporated to guarantee that, for at least 85-95% of compounds, the predicted k-distance lies within the convergence region. The best-performing models are made publicly available through an open-access web application.

Efficiency and selectivity of electrochemical reactions are controlled by micro-environments within the electric double layer (EDL) at the electrode-electrolyte interface. In electrocatalysis, additives can direct the interfacial structure, enhancing activities. Our current level of understanding of the fundamental interactions between the solvent, the electrolyte, and additives at the electrode surface under potential control are limited. This makes a priori predictions of the EDL structure challenging. Vibrational Sum Frequency Generation (VSFG) spectroscopy allows for observation of interface-specific vibrational signatures from which interfacial species may be identified and their orientation determined, providing a way to study the fundamental behaviour of electrified interfaces. We exploit this to study the structure of acetonitrile (CH3CN) in the presence of H2O and N-methyl-2-pyrrolidone (NMP) at a gold electrode under potential control. At low concentrations of H2O (300 ppm), the VSFG signatures of CH3CN are weak and become increasingly apparent as the concentration of H2O increases. We conclude that this is a result of the formation of an interfacial layer with increased net ordering of CH3CN molecules due to hydrogen bonding with H2O disrupting the microstructured CH3CN environment. At low concentrations of H2O, NMP accumulates at the negatively charged electrode surface, disrupting the CH3CN structure; however, addition of H2O perturbs the NMP structure, leading to an ordered CH3CN interfacial layer being formed.

Fast charging of lithium metal battery (LMB) is challenged by the sluggish Li+ diffusion in liquid electrolyte, resulting in excessive lithium dendrites growth issue. Towards overcoming this problem, here, we propose and demonstrate a new strategy for ultrafast Li+ transport in liquid LMB based on electronegative nanochannels (EN) in the functional separator. Experimental and computational results demonstrate that Li+ prefers to stay on the inner surface of the EN, with Grotthuss-like multiple ion collaborative transport rather than classical isolated ion random jumping, leading to ultrafast Li+ transport. As a result, the EN separator delivers a superior high Li+ conductivity (similar to 1 mS cm(-1)), and effectively stabilizes the lithium metal anode for 2000 h at a high current density of 5 mA cm(-2). The EN separator significantly improves the rate performance of the LMB (Li parallel to LiFePO4), whose discharge capacity reaches more than 90 mAh g(-1) at a high rate of 10 C, with a retention rate of up to 73.9% after 100 cycles, much higher than commercial polyolefin separators. These results demonstrate the critical role of the EN separator in enabling ultrafast Li+ transport and boosting both performance and stability in high-rate LMBs, pointing the way to further rational developments in the area.

The long-standing challenge in resolving the atomic-scale threshold switching mechanism in amorphous chalcogenides, fundamental constraint on further development of promising memory technologies, stems from their intrinsic structural disorder. Here, we overcome this pivotal challenge by capturing electric-field-driven dipolar ordering in amorphous GeSe through combined atomic-resolution angstrom-beam electron diffraction and field-coupled ab initio molecular dynamics. Electric fields induce anti-parallel displacements of Ge ( + 0.23 Å) and Se ( - 0.21 Å) atoms within picoseconds, aligning dipoles into one-dimension chains. These polarity-locked chains, evidenced by two distinct diffraction spots (1.95 Å spacing), guide conductive filament growth perpendicular to chain alignment. This mechanism enables direct harnessing of dipole-originated threshold voltage asymmetry in selector-only memory, achieving dual functionality through single-material engineering. This field-induced non-Arrhenius process squashes thermal activation barriers, enabling dipolar-order-driven switching within the picosecond regime thus breaking the thermal speed limit for resistive switching. Our findings establish a pathway to atomic-scale dipole control for ultrafast storage-class memory.

HfO2 thin films are recognized as pivotal materials for next-generation ferroelectric memories, and extensive experimental efforts have been dedicated to defect-engineering HfO2-based systems towards tailored ferroelectric properties. However, the microscopic mechanisms through which excess electrons modulate the defect states and doping behavior in HfO2 remain not fully understood, which has slowed progress in the field. To fill this gap, we investigate the interaction mechanisms between aliovalent dopants and oxygen vacancies (VO) in HfO2 by subspace corrected (PBE+U functional) density functional theory simulations. Our results reveal that the extra charge introduced by trivalent dopants forms a small polaron localized on a tricoordinated oxygen atom, producing a deep empty defect state within the HfO2 band gap. This deep defect state can interact with the excess electrons generated by oxygen vacancies, thereby enhancing the stability of the three-coordinated oxygen vacancy (VO3) configuration compared to the four-coordinated one (VO4). The introduction of VO4 lowers the local polarization-switching barrier near a statistical accumulation of vacancies by 13%, while VO3 produces a more pronounced reduction of 60%, corresponding to a minimum barrier of 0.12eV/u.c. The stabilized VO3 center effectively reduces the ferroelectric switching barrier in the Pca21 phase by promoting reduced atomic displacements and lattice distortions, significantly decreasing the coercive field of HfO2. These findings provide critical insights for advancing the fundamental understanding of HfO2 materials and establishing design guidelines for constructing defect-tolerant ferroelectric devices through targeted defect engineering.

Extensive research efforts have been concentrated into the conversion of CO2 into value-added chemicals as it provides a route to a circular carbon economy. Electroreduction of CO2 on Au surfaces allows for the selective transformation of CO2 into CO via carbon dioxide reduction reaction (CO2RR), and the catalytic activity depends on the concentration and identity of cations present at the electrode-electrolyte interface. Experimental reports performed under typical CO2RR-operating conditions have widely shown that the CO2RR is enabled by the presence of metal or organic cations in the cathodic interfacial microenvironment. A remaining question is to address if CO2RR can occur in the absence of metal or organic cations and, if so, what the mechanism may be. Here, we show that CO2 can be electrochemically reduced to CO on Au in acidic electrolytes rigorously controlled to avoid the presence of metal and organic cations and systematically suggest the important contributions allowing this reaction to proceed. The formation of CO is confirmed by both qualitative and quantitative methods using potentiodynamic CO-stripping scans and chromatography-assisted constant potential electrolysis. Calculations indicate that H3O+ is able to stabilize the formation of *CO2 -, albeit at more negative potentials than when an alkali metal cation is present. Spectroelectrochemical experiments show that the electric field at the interface is reduced when metal cations are not added, indicating that the decreased field stabilization of intermediates could play an important role in increased overpotential required for the CO2RR to occur.

Information can be stored in magnetic materials by encoding with the direction of the magnetic moment of elements. A figure of merit for these systems is the energy needed to change the information rewrite the storage by changing the magnetic moment. Organic molecules offer a playground to manipulate spin order, with metallo molecular interfaces being a promising direction for sustainable devices. Here, we demonstrate a spin reorientation transition in molecular interfaces of high magnetisation 3d ferromagnetic films due to a competition between a perpendicular magnetic anisotropy (PMA) induced by a heavy metal that dominates at high temperatures, and an in-plane anisotropy generated by molecular coupling at low temperatures. The transition can be tuned around room temperature by varying the ferromagnet thickness (1.4 to 1.9 nm) or the choice of molecular overlayer, with the organic molecules being C60, hydrogen and metal (Cu, Co) phthalocyanines. Near the transition temperature, the magnetisation easy axis can be switched with a small energy input, either electrically with a current density of 10^5 A per cm2, or optically by a fs laser pulse of fluence as low as 0.12 mJ per cm2, suggesting heat assisted technology applications. Magnetic dichroism measurements point toward a phase transition at the organic interface being responsible for the spin reorientation transition.

HfO2-based ferroelectric films have demonstrated great potential in nonvolatile memory, sensors, and energy harvesting applications. Although the ferroelectricity of HfO2 thin films can persist at the nanoscale, depolarization effects often lead to polarization degradation or even complete suppression. The underlying physical mechanisms governing this phenomenon remain controversial. Here, the depolarization mechanism of HfO2 films was thoroughly explored based on first-principles calculations, and results reveal that surface phase transitions play a vital role in the depolarization process. Although ferroelectric bulk phases for both Pca21 and Pmn21 are stable, out-of-plane ferroelectric (010) Pca21 film is thermodynamically unstable and transforms into P21/c spontaneously via an effectively barrierless twisting pathway. Notably, only out-of-plane electric polarization is reduced, while the in-plane one remains. Moreover, the tensile strain induced in HfO2 films by realistic substrates such as La1-xSrxMnO3 (x approximate to 0.2 similar to 0.4) induces a transformation of the film from the paraelectric P21/c phase to the antiferroelectric Pbcn one. Subsequently, during the wake-up process, the Pbcn phase can transition into the ferroelectric phase through a low-energy barrier. This study offers insights into the depolarization mechanisms in HfO2-based ferroelectrics and presents strategies for optimizing interfacial properties and tuning phase structures, thereby providing valuable theoretical guidance for enhancing phase stability in hafnium-based ferroelectric thin films.

The discovery of ferroelectric phases in HfO 2 offers insights into ferroelectricity. Its unique fluorite structure and complex polarization switching pathways exhibit distinct characteristics, challenging conventional analysis methods. Combining group theory and first-principles calculations, we identify numerous unconventional electric polarization switching pathways in HfO 2 with energy barriers of 0.32 to 0.57 eV as a function of the different shift in the suboxygen lattices. In total, we identify 47 switching pathways for the orthorhombic phase, corresponding to the left cosets of the F m 3 ¯ m group with P c a 2 1 group. Contrary to the conception that the tetracoordinated oxygen (O IV ) layers are inactive, our result demonstrates that both the tricoordinated oxygen (O III ) and O IV can be displaced, leading to polarization switching along any axial direction. The multiple switching pathways in HfO 2 result in both 180° polarization reversal and the formation of 90° domains observed experimentally. Calculations show that specific switching pathways depend on the orientation of the applied electric field relative to the HfO 2 growth surface. This allows HfO 2 to automatically adjust the in-plane polarization direction under an out-of-plane electric field, thereby maximizing the out-of-plane component and contributing to the wake-up process. These findings redefine the roles of O III and O IV layers, clarify unconventional switching pathways, and enhance our understanding of electric field response mechanisms, wake-up, and fatigue in ferroelectrics.

Metal-organic molecule interfaces have given rise to a wide range of magnetic phenomena. These effects arise due to spin-polarized charge transfer and enhanced exchange interaction at metallo-molecular hybridization sites, where tunability via electric fields beyond ferroelectric interfaces remains to be demonstrated. Here, we explore manipulating the magnetism of cobalt with the intrinsic electric field generated at C60/phthalocyanine heterojunctions, a combination commonly used in organic photovoltaics. The results give evidence for a C60 layer thickness-dependent control of hybridization effects on cobalt. We find that the heterojunctions may attenuate the hybridization effects, with changes in coercivity and magnetization due to the built-in electric field. An emergent exchange bias is attributed to an enhanced Rashba interaction for thicker C60 layers. Our study clarifies some of the questions in the field of molecular "spinterface" physics and demonstrates that internal electric field generation is a promising method for manipulation of metallo-molecular interfaces up to room temperature.

The unique structural configuration of amorphous nanomaterials, characterized by their disordered atomic arrangements, highly exposed active sites, and isotropic homogeneity, enables exceptional catalytic performance that bridges the gap between homogeneous and heterogeneous catalysis. In this work, an amorphous CuPd catalyst was fabricated through incorporating Cu ions into the disordered Pd lattice, creating an amorphous monolayer architecture with engineered hydrogen transport pathways. The precisely modulated atomic/electronic configuration optimizes the adsorption configuration and bonding strength between substrate/intermediates and catalysts surfaces. The amorphous catalyst achieves 96.2% selectivity at 99.1% conversion under mild conditions, with a time of flight of 6004 hour-1. These results demonstrate that amorphous architectures, with their disordered atomic arrangements, uniformly distributed active sites, and tunable adsorption energetics, establish a generalized design framework for high-performance catalysts, achieving superior selectivity and activity compared to crystalline systems.

In nanotechnology-based cancer therapy, modulating electronic states of nanomaterials is crucial for influencing spatiotemporal dynamic behaviors of intracellular reduction-oxidation and redox homeostasis. Although rare-earth transition metals with 4f electrons present electronic energy levels suitable for electronic modulation, its practical realization is challenging due to strong 4f electron localization. Theoretical studies indicate that amorphization can significantly alter the electronic states of the 4f-dominated nanomaterials. However, the isotropic nature of disordered structures poses challenges for morphology and dimensional regulation of amorphous nanomaterials, which is important in tumor therapy. In this study, we designed and synthesized amorphous Gd(OH)3 nanocages with regulated electronic states for antitumor therapy. The reduction of the Gd-O coordination number in the amorphous structure significantly diversifies the spatial occupancy, alters the electronic states, and enhances hole delocalization, thereby boosting the redox capability of the originally inert Gd3+ compound (half-filled 4f7 orbit). This results in unexpected peroxidase (POD)-like catalytic activity, with a Kcat of 3.49 × 104 s-1, which is an order of magnitude higher than that of the natural HRP enzyme. The amorphous Gd(OH)3 nanocages also show impressive antitumor effects both in vitro and in vivo, demonstrating that amorphization is an effective strategy for modulating the electronic states of rare earth elements and unlocking new catalytic and biomedical potential for advanced synthetic nanozymes.

Catalysts achieve changes in the rate through modification of the free energy of adsorbed intermediates and transition states (TrS). Binding energies of intermediates and TrS are strongly correlated, and modifications in catalyst composition are often ineffective in breaking these correlations, leading to minimal change in rate. Such scaling relationships are reported throughout catalysis. The surface spin state of a magnetic metal can change adsorption energies, offering a way to overcome scaling relationships. However, experimentally, this approach appears reliant on the use of ferromagnetic materials, limiting applicability. Here, we show that tunable changes in electrocatalytic activity for the hydrogen evolution reaction (HER) can be achieved at (originally) nonmagnetic metals (Au and Pt) through the use of a multilayer electrode structure that contains a ferromagnetic alloy (CoB) beneath a thin (5-20 nm) film of Pt or Au. Analysis of the dependence of the catalytic current on the thickness of the Au or Pt capping layer and on the direction of the stray magnetic field allows us to rule out the presence of magnetohydrodynamic effects. Instead, we conclude that transfer of ferromagnetism from the ferromagnet to the Au or Pt takes place through proximity-induced magnetism (PIM) via exchange interactions and/or a spin polarized current. Density Functional Theory simulations trace changes in the breaking of the scaling relationship for the Tafel HER mechanism. Overall, our experiments show that thin-film electrodes, based on routine structures from the spintronics community, are a potentially versatile platform for achieving spin-polarized catalysis at originally nonmagnetic metals.

An electric bias can shift the Fermi level along the Dirac cone of a topological insulator and modify its charge transport, but tuning the electronic states and spin-orbit interaction (SOI) without destroying the surface topology is challenging. Here, we show that thin film Bi2Se3/n-p (p-n) molecular diodes form ordered interfaces where charge transfer and orbital re-hybridisation result in a decrease (increase) of the carrier density and improved mobility. In Bi2Se3 the spin-orbit lifetime, t_so, is 0.13 ps, which is comparable to the strongest spin-orbit materials. This lifetime drops further to 0.06 ps (0.09 ps) with the addition of p-n (n-p) molecular diodes, at the limit of measurable values. This strengthened spin-orbit interaction occurs even though molecules are made of light elements and increase the mean free path of the charge carriers by almost 50

The adhesive strength at metal-organic interfaces is crucial to their functional integrity in technological devices. Despite substantial progress over the years, current solutions to improve the adhesion properties at such interfaces may not be sufficient to meet future demands. This scenario is challenging to the research community, demanding an improved atomistic-level understanding of the fundamental processes that rule the adhesive properties between metals and polymers. Unfortunately, the inherent structural complexity of these interfaces and the lack of consensus on the best experimental practices and characterization protocols complicate the reproducibility and atomistic interpretation of measurements. To contribute to addressing this knowledge gap, here we use ab initio molecular dynamics simulations to investigate the intricacies of the bonding structure for atomic models of Cu/Kapton films, an archetypal example of a metal/polymer interface. The simulations uncover a complex dependence of the interfacial electron transfer and interaction energy on the number of Cu atoms in direct contact with the Kapton polymeric chains. Relevant to the prospect of enhancing the adhesive properties, we demonstrate that uniaxial tensile strain of Cu/Kapton films between 7 and 11% induce bond breaking of only those Kapton chains in direct contact with the Cu atoms. This bond breaking leads to the formation of bonds with the surrounding Cu atoms, which increase the adhesion strength of the interface. Notably, Kapton chains not in contact with the Cu atoms withstand the applied strains, preserving the structural integrity of the film. These findings and associated insights into previously overlooked aspects of Cu/Kapton adhesion are valuable additions to ongoing efforts toward the optimization of metal-polymer interfaces.

Hafnium oxide (HfO₂) has emerged as a transformative material for next‐generation non‐volatile memory technologies due to its unique ability to exhibit ferroelectricity in ultrathin films. Its practical application is critically hindered by polarization fatigue and depolarization phenomena, while the inherent complexity of these transitions between ferroelectric and paraelectric state in HfO₂ has posed significant challenges. Here, symmetry analysis and with first‐principles calculations is leveraged to systematically explore all potential transition pathways from the ferroelectric oIII/oIV phases to the paraelectric mI/mII phases. The results demonstrate that multiple‐pathways involving intermediate phases, such as , , and , require relatively high energy barriers ranging from 0.33 to 0.71 eV per unit cell. In contrast, a direct transition from oIII to mI requires overcoming an energy barrier of only 0.11 eV per unit cell, suggesting that ferroelectric fatigue can occur along the direct pathway rather than multiple ones. This direct transition induces an in‐plane expansion of ≈4%, thus applying in‐plane confinement or compressive strain can be effective in suppressing fatigue. These findings provide a comprehensive framework for elucidating the phase transition dynamics and mechanisms underlying ferroelectric fatigue in HfO₂, offering critical insights for optimizing its integration into advanced memory technologies.

In the realm of perovskite materials, organic molecules situated at the A site play a critical role in stabilizing the structure through specific orientations and weak interactions with the inorganic framework. These polar interactions significantly influence the optoelectronic properties of perovskites, and the introduction of polar molecules can disrupt the inherent polarization, thereby altering the material performance. The research primarily focuses on the relationship between the length and width of these organic cations and their polar inductive effects. Overall, the interplay between the chain length, molecular width, and dipole moments was shown to significantly affect the lifetime of MAPbI3 materials. Key findings indicate that non-radiative recombination, which is a major energy loss mechanism in solar cells, is intrinsically linked to the variations of hydrogen bonds and PbI6 octahedral distortion. The analysis revealed a strong negative correlation between octahedral angles, highlighting the complex relationship between these variables and their collective effects on charge carrier dynamics.