Atomic Mechanisms Research Articles

Why is Dimeric 3D Domain Swapping in Antibody Light Chains Missing from the Solution? Atomistic Insights Mechanisms.

Misfolding of antibody light chains can lead to systemic light chain amyloidosis, which is associated with misfolding and aggregation. The antibody light chain may engage in 3D domain swapping within the variable region (#4VL) through hydrogen bonding (HB) interactions, potentially forming the tetramer, as revealed in solution and crystal structures. However, the 3D-domain swapping (3D-DS) dimers could not be detected experimentally. This study investigates the absence of 3D-DS using computational approaches, focusing on structural dynamics, solvation effects, and stability relevant to the loss of 3D-DS. Microscale molecular dynamics simulations of #4VL and 3D-DS confirm that native HB interactions are essential to maintain β-sheet structures in both #4VL and 3D-DS. A flickering native HB interaction in the 3D-DS system, caused by repulsive interaction with water molecules in the hydrophobic region, leads to intramolecular breathing motions and oligomerization in another 3D-DS. Structural dynamics of the 3D-DS dimer in long-run simulations were analyzed using the newly developed integrated solvation-based principal component analysis (3D-RISM/PCA) and density-based spatial clustering of applications with noise, confirm that if the 3D-DS cannot form the tetramer within the breathing motion process, the 3D-DS will collapse. This finding provides insights into why the 3D-DS dimer is missing from the solution and can be used to design and develop 3D-DS in other antibodies.

Kinetics and Dynamics of Cyclopentanone Thermal Decomposition in Gas Phase.

Cyclopentanone is a potential bio-fuel which can be produced from bio-mass. Its gas phase dissociation chemistry has attracted several experimental and theoretical investigations. In the photochemical and thermal decomposition studies of cyclopentanone, ethylene and carbon monoxide were found to be dominant reaction products along with several other compounds in smaller quantities. For the formation of ethylene and carbon monoxide, a concerted mechanism has been proposed as primary reaction pathway. In addition, a step-wise mechanism involving ring-opened radical intermediate has also been considered. The present work reports gas phase thermal decomposition of cyclopentanone at high temperatures investigated using electronic structure theory methods, Rice-Ramsperger-Kassel-Marcus (RRKM) rate constant calculations, and Born-Oppenheimer direct classical trajectory simulations. The trajectory calculations were performed on density functional PBE96/6-31+G* potential energy surface using initial conditions selected from fixed energy normal mode distributions. Simulations showed that ethylene and carbon monoxide formed primarily via the concerted mechanism confirming the earlier predictions. In addition, stepwise pathways were also observed for same products in lower fraction of trajectories. Furthermore, several other reaction products in smaller quantities and new mechanistic pathways were observed. The computed RRKM rate constants and simulation data are agreement with experimental results and detailed atomic level dissociation mechanisms presented.

Microstructural evolution mechanism and mechanical properties of La and Gd on AZ91 alloy: Experiments and first-principles calculations

The morphology and thermal stability of the Al-RE phase in Mg-Al-RE alloys are critical to their mechanical properties, particularly at elevated temperatures. In this study, AZ91, AZ91–2La, and AZ91–2La-0.6Gd alloys were prepared via gravity casting and characterized using optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS) and transmission electron microscopy (TEM). The results indicate that adding La reduces the amount of the Mg17Al12 phase and introduces a long acicular Al11La3 phase. Further addition of minor amounts of Gd transforms the long acicular Al11La3 phase into a short rod-like Al11RE3 phase. Tensile tests and fracture analyses at both room and elevated temperatures reveal that the AZ91–2La-0.6Gd alloy exhibits exceptional tensile properties. First-principles calculations were used to study the modification mechanism of Gd atoms on the Al11La3 phase. Adsorption calculations show that Gd atoms stably adsorb on the Al11La3 (001) growth surface, altering its growth characteristics. These calculations also investigated the thermal stability and formation enthalpy of intermetallic phases in Mg-Al-La-Gd alloys. Additionally, the complex alloying reactions during the solidification of the Mg-Al-La-Gd multi-element alloy system were simplified. This study provides new insights into the interaction mechanisms of rare earth (RE) elements in Mg-Al series alloys. It also offers a new approach for designing heat-resistant Mg-Al-RE alloys.

Atomistic mechanisms of the regulation of small-conductance Ca2+-activated K+ channel (SK2) by PIP2

Small-conductance Ca2+-activated K+ channels (SK, KCa2) are gated solely by intracellular microdomain Ca2+. The channel has emerged as a therapeutic target for cardiac arrhythmias. Calmodulin (CaM) interacts with the CaM binding domain (CaMBD) of the SK channels, serving as the obligatory Ca2+ sensor to gate the channels. In heterologous expression systems, phosphatidylinositol 4,5-bisphosphate (PIP2) coordinates with CaM in regulating SK channels. However, the roles and mechanisms of PIP2 in regulating SK channels in cardiomyocytes remain unknown. Here, optogenetics, magnetic nanoparticles, combined with Rosetta structural modeling, and molecular dynamics (MD) simulations revealed the atomistic mechanisms of how PIP2 works in concert with Ca2+-CaM in the SK channel activation. Our computational study affords evidence for the critical role of the amino acid residue R395 in the S6 transmembrane segment, which is localized in propinquity to the intracellular hydrophobic gate. This residue forms a salt bridge with residue E398 in the S6 transmembrane segment from the adjacent subunit. Both R395 and E398 are conserved in all known isoforms of SK channels. Our findings suggest that the binding of PIP2 to R395 residue disrupts the R395:E398 salt bridge, increasing the flexibility of the transmembrane segment S6 and the activation of the channel. Importantly, our findings serve as a platform for testing of structural-based drug designs for therapeutic inhibitors and activators of the SK channel family. The study is timely since inhibitors of SK channels are currently in clinical trials to treat atrial arrhythmias.

Biodegradable copper-iodide clusters modulate mitochondrial function and suppress tumor growth under ultralow-dose X-ray irradiation

Both copper (Cu2+/+) and iodine (I−) are essential elements in all living organisms. Increasing the intracellular concentrations of Cu or I ions may efficiently inhibit tumor growth. However, efficient delivery of Cu and I ions into tumor cells is still a challenge, as Cu chelation and iodide salts are highly water-soluble and can release in untargeted tissue. Here we report mitochondria-targeted Cu-I cluster nanoparticles using the reaction of Cu+ and I− to form stable bovine serum albumin (BSA) radiation-induced phosphors (Cu-I@BSA). These solve the stability issues of Cu+ and I− ions. Cu-I@BSA exhibit bright radioluminescence, and easily conjugate with the emission-matched photosensitizer and targeting molecule using functional groups on the surface of BSA. Investigations in vitro and in vivo demonstrate that radioluminescence under low-dose X-ray irradiation excites the conjugated photosensitizer to generate singlet oxygen, and combines with the radiosensitization mechanism of the heavy atom of iodine, resulting in efficient tumor inhibition in female mice. Furthermore, our study reveals that BSA protection causes the biodegradable Cu-I clusters to release free Cu and I ions and induce cell death by modulating mitochondrial function, damaging DNA, disrupting the tricarboxylic acid cycle, decreasing ATP generation, amplifying oxidative stress, and boosting the Bcl-2 pathway.

Intrinsic Ferroelectric Switching in Two-Dimensional α-In2Se3.

Two-dimensional (2D) ferroelectric semiconductors present opportunities for integrating ferroelectrics into high-density ultrathin nanoelectronics. Among the few synthesized 2D ferroelectrics, α-In2Se3, known for its electrically addressable vertical polarization, has attracted significant interest. However, the understanding of many fundamental characteristics of this material, such as the existence of spontaneous in-plane polarization and switching mechanisms, remains controversial, marked by conflicting experimental and theoretical results. Here, our combined experimental characterizations with piezoresponse force microscope and symmetry analysis conclusively dismiss previous claims of in-plane ferroelectricity in single-domain α-In2Se3. The processes of vertical polarization switching in monolayer α-In2Se3 are explored with deep-learning-assisted large-scale molecular dynamics simulations, revealing atomistic mechanisms fundamentally different from those of bulk ferroelectrics. Despite lacking in-plane effective polarization, 1D domain walls can be moved by both out-of-plane and in-plane fields, exhibiting avalanche dynamics characterized by abrupt, intermittent moving patterns. The propagating velocity at various temperatures, field orientations, and strengths can be statistically described with a universal creep equation, featuring a dynamical exponent of 2 that is distinct from all known values for elastic interfaces moving in disordered media. This work rectifies a long-held misunderstanding regarding the in-plane ferroelectricity of α-In2Se3, and the quantitative characterizations of domain wall velocity will hold broad implications for both the fundamental understanding and technological applications of 2D ferroelectrics.

Exploring Protonation State, Ion Binding, and Photoactivated Channel Opening of an Anion Channelrhodopsin by Molecular Simulations.

Channelrhodopsins are light-gated ion channels with a retinal chromophore found in microbes and are widely used in optogenetics, a field of neuroscience that utilizes light to regulate neuronal activity. GtACR1, an anion conducting channelrhodopsin derived from Guillardia theta, has attracted attention for its application as a neuronal silencer in optogenetics because of its high conductivity and selectivity. However, atomistic mechanisms of channel photoactivation and ion conduction have not yet been elucidated. In the present study, we investigated the molecular characteristics of GtACR1 and its photoactivation processes by molecular simulations. The QM/MM RWFE-SCF method which combines highly accurate quantum chemistry calculations with long-time molecular dynamics (MD) simulations were used to model protein structures of the wild-type and mutants with different protonation states of key groups and to calculate absorption energies for verification of the models. The QM/MM modeling together with MD simulations of free-energy calculations favors protonation of a key counterion carboxyl group of Asp234 with a strong binding of a chloride ion in the extracellular pocket in the dark state. A channel open state was also successfully modeled by the QM/MM RWFE-SCF free-energy optimizations, providing atomistic insights into the channel activation mechanism.

Molecular Dynamics Simulation and Experimental Study of the Mechanical and Tribological Properties of GNS-COOH/PEEK/PTFE Composites.

Molecular dynamics (MD) simulations were first employed to achieve the optimal sintering temperature of carboxyl-functionalized graphene (GNS-COOH)-modified polyether ether ketone (PEEK)/polytetrafluoroethylene (PTFE) composites. A model of GNS-COOH/PEEK/PTFE composites was constructed to simulate the effects of different sintering temperatures on the mechanical and tribological properties, as well as their underlying atomic mechanisms. Samples of PTFE composites were prepared and characterized through experimental methods. Results revealed that the sintering temperature significantly affects the intermolecular forces, mechanical properties, and tribological characteristics of the composites. The agglomeration of the PEEK/PTFE composite matrix was effectively mitigated by introducing GNS-COOH. When the sintering temperature was controlled at 360 °C, the compressive strength of GNS-COOH/PEEK/PTFE composites was improved compared to GNS/PEEK/PTFE composites, albeit with a slight reduction in wear resistance. This study provides a theoretical reference for the preparation process and performance evaluation of new materials.

Atomic effect and mechanism of different hydrogen content on superlubricity properties of H-DLC films

Hydrogen atoms play a pivotal role in achieving superlubricity in DLC films. Nevertheless, the inherent limitations in analytical testing techniques obscure the mechanisms by which hydrogen atoms achieve superlubricity in DLC films. Furthermore, direct evidence supporting the widely accepted mechanism of hydrogen passivation remains elusive. Therefore, we used ReaxFF MD simulations to investigate the effects of different hydrogen content on the tribological and wear properties of hydrogen-doped H-DLC films. Hydrogen atoms diffuse from the DLC films and gradually accumulate on the friction surface during the sliding, effectively passivating and inhibiting the C–C bonds at the interface. This reduces cross-linking between H-DLC films, consequently loweringfrictiontemperature significantly during the sliding. A significant release of hydrogen atoms during the friction process weakens the strength of machinery of H-DLC films, potentially causing structural failures under hydrogen-rich conditions, with the released hydrogen atoms subsequently occupying structural voids within films. At the microscopic scale, the friction of H-DLC film decreases with the increase of hydrogen content, but when the hydrogen content reaches 40 % or above, the local collapse of the system will be caused, resulting in the failure of superlubricity. Finally, the friction and wear of H-DLC film under high hydrogen conditions will rebound.

Surface complexation of rare earth elements on goethite in sea-floor hydrothermal environment: Insight from first principles simulations

Deep-sea mud shows tremendous resource potential for rare earth elements (REEs) and its formation is closely associated with sea-floor hydrothermal activities. Iron (oxyhydr)oxides link the sources and sinks of REEs in sea-floor hydrothermal systems. However, the complexation mechanisms of REEs on iron (oxyhydr)oxides have not been well understood yet. In this study, by using the first principles molecular dynamics technique, we first calculated the pKa’s of surface groups on goethite (110) surface at elevated temperatures relevant to sea-floor hydrothermal systems and then evaluated the complexation structures and free energies of REEs on goethite (110) and (010) surfaces using the method of constraint by taking Sc3+, Y3+, and La3+ as model REE cations. The results show that REE complexation occurs in mildly acidic to neutral conditions. The most thermodynamically stable complexes of REEs are bidentate complexes on two neighboring FeOH sites on goethite (110) surface and tridentate complexes on two neighboring FeOH sites plus one Fe2OH site on goethite (010) surface. Sc3+ complexes match the goethite lattice and can be incorporated into the lattice. The stabilities of REE complexes increase with the distance from hydrothermal vents. Complexation of Y3+ is less favored on goethite compared to other REEs whereas Sc3+ prefers complexation on goethite (010) surface and La3+ exhibits similar stabilities on both (010) and (110) surfaces. The derived atomic level complexation mechanisms would be helpful for the interpretation of experimental data and the prediction of REEs’ behavior in the sea-floor. The findings presented here provide valuable insights into REEs fractionation and enrichment in deep-sea muds.

Effect of element doping on the structural stability, magnetic properties and electronic structure of SmCo5-based rare earth permanent magnets

Doping transition metals has been proven as an effective method to enhance the performance of Sm-Co based rare earth permanent magnets. However, due to the complex interactions involved, the specific effects on magnetic properties, atomic occupancy preferences and structural stability mechanisms are still to be further investigated. In this study, we systematically investigated the influence of various transition metal dopants on the structural stability, magnetic properties and electronic structure of SmCo5 rare earth permanent magnet using first-principles calculations. Our calculations show that Ti, V, Cr, Mn, Ni, Cu, Zn elements preferentially occupy the 3 g site, while Sc and Zr tend to occupy the 1a site, and Fe elements have a preference for the 2c site. Regarding structural stability, doping with Sc, Cr, Mn, Fe, Ni, Cu, Zn and Zr all contribute to enhancing structural stability, while Ti and V doping exhibit adverse effects. Magnetic calculations indicate that doping with Mn and Fe significantly increases the total magnetic moment of the SmCo5 system. Notably, at a high doping concentration of 60 at%, the Ni and Zn-doped systems exhibit an exceptionally large magnetocrystalline anisotropy energy Additionally, a change in the magnetic easy axis direction occurs when the doping concentrations of Cr, Fe, Cu and Zn reach 60 at%, 40 at%, 40 at% (and 60 at%), 40 at% (and 60 at%), respectively. Our work provides important theoretical guidance for further optimizing the performance of Sm-Co based rare earth permanent magnets.

Development of Highly Efficient Lamb Wave Transducers toward Dual-Surface Simultaneous Atomization.

Highly efficient surface acoustic wave (SAW) transducers offer significant advantages for microfluidic atomization. Aiming at highly efficient atomization, we innovatively accomplish dual-surface simultaneous atomization by strategically positioning the liquid supply outside the IDT aperture edge. Initially, we optimize Lamb wave transducers and specifically investigate their performance based on the ratio of substrate thickness to acoustic wavelength. When this ratio h/λ is approximately 1.25, the electromechanical coupling coefficient of A0-mode Lamb waves can reach around 5.5% for 128° Y-X LiNbO3. We then study the mechanism of droplet atomization with the liquid supply positioned outside the IDT aperture edge. Experimental results demonstrate that optimized Lamb wave transducers exhibit clear dual-surface simultaneous atomization. These transducers provide equivalent amplitude acoustic wave vibrations on both surfaces, causing the liquid thin film to accumulate at the edges of the dual-surface and form a continuous mist.

Atomistic understanding of ductile-to-brittle transition in single crystal Si and GaAs under nanoscratch

Ensuring ductile removal in a grinding process is crucial for achieving the desired finish on a hard and brittle single crystal. This study provides new insights into the material removal processes in Si and GaAs single crystals, exploring their deformation behaviour using Berkovich and Conical tips to replicate contact from a fixed abrasive grit. Experimental observations are compared with Molecular Dynamic (MD) simulations to uncover the atomistic deformation mechanisms during the ductile-to-brittle transition (DBT). Notable plastic deformation and minimal cracking were consistently observed in Si, irrespective of the tips used. MD simulations supported this observation, revealing pronounced chip formation indicative of ductile material removal. The resistance to cracking in Si was attributed to amorphization induced by localized high contact stresses. In contrast, GaAs showed a propensity for cracking, with MD simulations revealing dislocation and slip band formation, and cracks emerging in the areas of substantial plastic deformation. These findings address phenomena not previously discernible in experimental studies due to the challenge of real-time observation. Moreover, the tip geometry was shown to significantly influence stress distribution, impacting deformation and crack formation in GaAs. This study also reveals limitations in predicting the critical depth for DBT in both Si and GaAs throught the amended Bifano, Dow, and Scattergood (aBDS) models and MD simulation, offering nuanced insights into these challenges that have not been extensively explored. It was found that the experimental results exceeded predictions by an order of magnitude. These discrepancies underscore the aBDS model's disregard for essential material properties and tip geometry, while the disparities between MD simulation and experiment are primarily attributed to the inherent limitations in the simulated length scales and challenges in detecting initial subsurface cracks.

Study on the atomic scale deformation mechanism of the h-BN coating nickel matrix composites

In this paper, molecular dynamics (MD) simulations are applied to study the contact mechanical behavior of hexagonal boron nitride (h-BN) coating/Ni matrix composites during nanoindentation, revealing the material deformation mechanism. A systematic study is carried out on the load-depth curve, temperature response curve, defect morphology, and dislocation density in indentation. The results show that the presence of h-BN coating increases the actual loading area of the matrix, effectively reduces the contact stress between the tip of the indenter and the specimen, and also induces the generation of high-density Shockley dislocations, which increases the dislocation entanglement and leads to the localized hardening of the composites, thus reducing the matrix damage. During the loading process, the temperature of the specimen before the destruction of the h-BN coating is significantly lower than that after the destruction, indicating that the coating tends to block the transfer of temperature to the interior of the specimen, preventing the occurrence of temperature-induced tissue phase changes inside the specimen, and providing good protection for the interior of the specimen.

Decoding ceramic fracture: Atomic defects studies in multiscale simulations

Microstructural atomic defects, including voids, cleavage, and inclusions, are commonly observed in alumina materials, and their impact on mechanical properties, such as fracture stress and toughness, is significant. In this paper, we introduce novel alumina models that incorporate experimentally observed void features. An atomic model is established to study the effects of micro-structural void features on fracture properties and atomic structure changes using molecular dynamics simulations. The electron backscatter diffraction and scanning electronic microscopy analysis of experimental samples are used to evaluate microstructural features that are used as inputs to the simulations (e.g., void aspect ratio, void angle). We apply an innovative Atomistic-to-Continuum (ATC) method based on Riemann sums to bridge atomic and continuum mechanics theories, evaluating the resistance of materials with atomic defects to crack propagation. The results show the greatest effects of pore angles on weakening mechanical properties such as peak strength and fracture energy density. The accuracy and efficiency of the ATC method in evaluating stress intensity factors are used to calculate the mechanical responses. Additionally, we establish a multiple layer perceptron neural network to evaluate the complex relationship between void features (aspect ratio, pore angle, relative distance) and typical fracture properties (fracture stress, critical stress intensity factor). A meta-analysis of these results from both machine learning methods and molecular dynamics simulations reveals the significant impact of each void feature on the sensitivity of typical fracture properties (peak strength, critical stress intensity factor at peak strength) and highlights the critical role of aspect ratio on fracture properties.

Disconnection units of twinning in body-centered-cubic metals

Twin boundary (TB) migration, facilitated by the motion of disconnections, plays a pivotal role in the deformation of body-centered cubic (BCC) crystals. Comprehending the migration rules of twinning disconnections (TDs) under shear stress is significant in elucidating the role of twin migration in BCC plasticity. Nevertheless, our understanding of the atomic structure and migration mechanics of TDs remains incomplete. In this study, we employ the theory of interfacial defects and molecular dynamics (MD) simulations to thoroughly investigate potential {112}[111] TDs in BCC tantalum (Ta). These TDs are characterized by their Burgers vectors, which were predicted through related dichromatic pattern analysis. We reveal that single-layer and double-layer TDs represent the fundamental building blocks (units) of multi-layer TDs. Their migration directions are entirely opposite under the same shear loading, and they cannot annihilate each other when they migrate “face to face”. Furthermore, these migration rules governing single-layer and double-layer TDs offer a comprehensive explanation for the complex composition and decomposition patterns observed among various multi-layer TDs. What's more, we demonstrated that TDs with zero Burgers vector can only be driven as a whole under coupled loading conditions. These findings significantly enhance our understanding of TB migrations in BCC metals.

The Role of Molecular Dynamics Simulations in Elucidating Interactions between Antimicrobial Peptides and Model Biological Membranes

In addressing the global problem of antimicrobial resistance, an emerging class of molecules called antimicrobial peptides (AMPs) are being widely studied. Their interactions with cell membranes are instrumental in their killing action, usually by forming pores or translocating to act on an internal target. Molecular dynamics (MD) simulations have played an essential role in understanding the atomistic mechanisms of such interactions. This review will highlight key findings from various MD studies, such as the formation of nanoaggregates and different types of pores. We will also discuss the role of selecting the membrane model composition, the level of detail in the simulation, and the choice of force field. It is evident in this review that our understanding of the interactions of AMPs and membranes has grown over the recent years through the help of MD simulations. Still, remaining concerns in MD studies of such systems must be addressed to gain more information.

Computational and Experimental Investigations of the Au and NiOOH Interface in the Oxygen Evolution Reaction

The transition to renewable energy sources is crucial for combating climate change, and hydrogen (H2) is a promising clean fuel. Electrolysis of water, specifically the oxygen evolution reaction (OER), is a key process for producing H2. Prior experimental results have shown that gold (Au) could improve the apparent activities of the OER electrocatalysts such as nickel hydroxide (Ni(OH)2) in alkaline electrolytes.1-3 However, the detailed interfacial atomic structure and mechanisms of the increased catalytic activity remain poorly understood.To understand the interfacial effect between Au and Ni(OH)2 in the OER process, our research uses the model system of Au nanoparticles (NPs) and nickel oxyhydroxide (NiOOH), which is the active phase of Ni(OH)2 layers in the OER, to investigate their interfacial interactions with both experimental and computational approaches. We hypothesize that the Au NPs on NiOOH enhances the OER activity by promoting electron transfer at the interface. Our studies involve computational analysis using Density Functional Theory (DFT) calculations to obtain the local density of states (LDOS), which can help us better visualize and compare the local electronic structure of NiOOH in the presence and in the absence of AuNPs. Two architectures of the Au and NiOOH interface will be investigated: Au NPs on a NiOOH film and NiOOH NPs on a Au film.Additionally, Bader analysis is employed to determine the Bader charge, offering a more detailed understanding of how electrons are distributed across the AuNPs/NiOOH interface. Furthermore, the catalytic efficacy of AuNPs on NiOOH is assessed through electrodepositions followed by cyclic voltammetry(CV) measurements. The experimental and computational results will be directly compared, and this research is expected to contribute to the insights of substrate and catalyst interactions for design of more efficient electrocatalysts.

Unveiling the intricacies of steel corrosion induced by chloride: Insights from reactive molecular dynamics simulation

Corrosion of reinforcing steels induced by chloride has long been a focal point of research, yet the atomic behavior and mechanism is not fully understood. In present study, we developed a reactive force field (ReaxFF) incorporating the Fe/Cl system based on Density Functional Theory calculations to elucidate atomic-scale behavior and mechanism underlying chloride-induced corrosion of reinforcing steel. Results from ReaxFF simulations employing this force field indicate that the initiation of steel corrosion is catalytically induced by chloride present in the outer layer, and the electron transfer between atoms is identified as a critical factor in corrosion. Specifically, Fe atoms become positively charged, detaching from the matrix surface and dissolving into the solution to form iron chloride compounds with surface Cl, while oxygen atoms turn negatively charged, progressively infiltrating the matrix and combining with Fe to create intricate iron oxide compounds. Furthermore, the entire dynamic process of corrosion oxidation on the surface of the ferritic matrix and the formation of product species has been fully captured. This ongoing corrosion process leads to significant matrix loss from metal surface and a reduction in structural integrity.

(Invited) Unveiling Fundamental Reaction Mechanisms at the Electrochemical Interface by Ab Initio Simulations

Direct experimental exploration of atomistic mechanisms governing electrocatalysis or wet corrosion at the solid-liquid interface is notoriously difficult. While fully parameter-free ab initio calculations have the potential to accurately elucidate such mechanisms, they encounter substantial conceptual challenges. Recent methodological breakthroughs, including the advent of efficient computational electrodes and the development of effective thermopotentiostats, overcame many of these limitations thus providing new research opportunities. This presentation outlines the fundamental concepts underlying these innovative methodologies and demonstrates their application in performing fully explicit calculations of structure and chemical reactions at electrified solid-water interfaces. The power of this approach in discovering new mechanisms will be demonstrated for fundamental electrochemical reactions such as metal dissolution and the hydrogen evolution reaction (HER). The identified mechanisms challenge existing understandings and empfasize the active involvement of water molecules in electrochemical reactions, challenging the perception that they are passive bystanders.