Development of a ReaxFF Reactive Force Field for Pt/Cl Systems with Application to Platinum Metal Etching with Chlorine and Hydrogen Chloride Gases.

In this study, we present the development of a ReaxFF Pt/Cl/H reactive force field designed to elucidate the etching process by Cl for Pt surfaces. The ReaxFF force field parameters were optimized based on a quantum mechanical training set, which included adsorption energies of Cl and dissociation of HCl on Pt(100) and Pt(111) surfaces, energy/volume relations of PtCl2 crystals, and Cl diffusion on Pt(100) and Pt(111) surfaces. The predictive capability of the force field was further established through molecular dynamics simulations, which investigated the interactions of Cl2 and HCl molecules with the (100) and (111) surfaces of c-Pt crystalline solid slabs. A comparative analysis revealed that the Pt (100) surface exhibited higher susceptibility to chlorination and etching, leading to a more dominant removal of surface Pt atoms, whereas the Pt (111) surface showed greater resistance to these processes. This resistance impeded the access of Cl atoms to the Pt surface, resulting in a slower formation of PtxCly molecules. The etching ratios between HCl and Cl2 were compared with experimental results, yielding satisfactory agreement. This indicates that the developed ReaxFF protocol serves as a valuable tool for studying atomistic-scale details of the etching process in platinum metal systems.

Implementing reactivity in molecular dynamics simulations with harmonic force fields.

The simulation of chemical reactions and mechanical properties including failure from atoms to the micrometer scale remains a longstanding challenge in chemistry and materials science. Bottlenecks include computational feasibility, reliability, and cost. We introduce a method for reactive molecular dynamics simulations using a clean replacement of non-reactive classical harmonic bond potentials with reactive, energy-conserving Morse potentials, called the Reactive INTERFACE Force Field (IFF-R). IFF-R is compatible with force fields for organic and inorganic compounds such as IFF, CHARMM, PCFF, OPLS-AA, and AMBER. Bond dissociation is enabled by three interpretable Morse parameters per bond type and zero energy upon disconnect. Use cases for bond breaking in molecules, failure of polymers, carbon nanostructures, proteins, composite materials, and metals are shown. The simulation of bond forming reactions is included via template-based methods. IFF-R maintains the accuracy of the corresponding non-reactive force fields and is about 30 times faster than prior reactive simulation methods.

Nanomaterials Research at a Primarily Undergraduate Institution: Transforming Nanorods, Undergraduate Research Communities, and Infrastructure.

Undergraduate research transforms student's conceptions of themselves as scientists and encourages participation and retention in science, technology, engineering, and mathematics (STEM) fields. Many barriers exist to carrying out scientifically impactful undergraduate research in nanomaterials at primarily undergraduate institutions (PUIs). Here, we share several practices and design principles that demonstrate pathways to overcome these barriers. Design of modular research projects with low entry barriers is essential. Postsynthetic transformation of nanoparticles is a field that enables such design and has been used successfully to advance nanoscience research while being achievable within undergraduate laboratories. Relatively large, inclusive research communities can be supported through the creation of opportunities with peer- and near-peer mentoring. We also share emerging strategies for enabling routine undergraduate access to transmission electron microscopy, which is one of the most mainstream characterization techniques in nanoscience yet is frequently absent from the infrastructure at undergraduate-focused institutions.

Advancing DBD Plasma Chemistry: Insights into Reactive Nitrogen Species such as NO2, N2O5, and N2O Optimization and Species Reactivity through Experiments and MD Simulations.

This study aims to fine-tune the plasma composition with a particular emphasis on reactive nitrogen species (RNS) including nitrogen dioxide (NO2), dinitrogen pentoxide (N2O5), and nitrous oxide (N2O), produced by a self-constructed cylindrical dielectric barrier discharge (CDBD). We demonstrated the effective manipulation of the plasma chemical profile by optimizing electrical properties, including the applied voltage and frequency, and by adjusting the nitrogen and oxygen ratios in the gas mixture. Additionally, quantification of these active species was achieved using Fourier transform infrared spectroscopy. The study further extends to exploring the aerosol polymerization of acrylamide (AM) into polyacrylamide (PAM), serving as a model reaction to evaluate the reactivity of different plasma-generated species, highlighting the significant role of NO2 in achieving high polymerization yields. Complementing our experimental data, molecular dynamics (MD) simulations, based on the ReaxFF reactive force field potential, explored the interactions between reactive oxygen species, specifically hydroxyl radicals (OH) and hydrogen peroxide (H2O2), with water molecules. Understanding these interactions, combined with the optimization of plasma chemistry, is crucial for enhancing the effectiveness of DBD plasma in environmental applications like air purification and water treatment.

Prediction of a Novel Electromechanical Response in Polar Polymers with Rigid Backbones: Contrasting Furan-Derived Nanothreads to Poly(Vinylidene Fluoride).

Syn furan nanothreads have all oxygen atoms arranged on one side of the thread backbone; these polar threads present intriguing opportunities in electromechanical response owing to their rigid ladder-like backbone. We retrained a C/H/O reactive force field to simulate their response to external electric field for both end-anchored individual threads and bulk nanothread crystals, contrasting the results to those for poly(vinylidene fluoride) (PVDF) polymer. Whereas the field induces a length-independent torque in PVDF through backbone rotation about σ bonds, furan-derived nanothreads generate a length-dependent torque by progressively twisting their rigid backbone. This mode of response couples the rotational history of the electric field to axial tension in the anchored thread. In simulations of densely packed syn furan nanothread crystals without anchors, the crystals pole in a field (∼3 GV/m at 300 K) similar to that seen in simulations of PVDF, suggesting that crystals of polar nanothreads can be ferroelectric.

Direct Fabrication of Atomically Defined Pores in MXenes Using Feedback-Driven STEM.

Controlled fabrication of nanopores in 2D materials offer the means to create robust membranes needed for ion transport and nanofiltration. Techniques for creating nanopores have relied upon either plasma etching or direct irradiation; however, aberration-corrected scanning transmission electron microscopy (STEM) offers the advantage of combining a sub-Å sized electron beam for atomic manipulation along with atomic resolution imaging. Here, a method for automated nanopore fabrication is utilized with real-time atomic visualization to enhance the mechanistic understanding of beam-induced transformations. Additionally, an electron beam simulation technique, Electron-Beam Simulator (E-BeamSim) is developed to observe the atomic movements and interactions resulting from electron beam irradiation. Using the MXene Ti3C2Tx, the influence of temperature on nanopore fabrication is explored by tracking atomic transformations and find that at room temperature the electron beam irradiation induces random displacement and results in titanium pileups at the nanopore edge, which is confirmed by E-BeamSim. At elevated temperatures, after removal of the surface functional groups and with the increased mobility of atoms results in atomic transformations that lead to the selective removal of atoms layer by layer. This work can lead to the development of defect engineering techniques within functionalized MXene layers and other 2D materials.

Exploring Gas-Phase Chemical Reactions in NH3/B2H6 Systems for Chemical Vapor Deposition Using Reactive Molecular Dynamics.

Hexagonal boron nitride (hBN) has attracted significant attention as a two-dimensional (2D) material due to its unique structure and properties. In this paper, we investigated the gas-phase reactions between B2H6 and NH3 and the reaction pathways potentially leading to the synthesis of hBN by using ReaxFF-based reactive molecular dynamics (MD) simulations. From the hundreds of chemical reaction pathways observed in these MD simulations, we extracted a highly reduced chemical kinetic model to describe the gas-phase mixture evolution in chemical vapor deposition of hBN using B2H6 and NH3 as precursors. The intent is to integrate this chemical model into future computational fluid dynamics (CFD) simulations of actual hBN deposition testing and production reactors to provide enhanced insights for experimental synthesis processes and reactor optimization. The chemical model of this study will serve as a stepping stone for large-scale simulations.

Mixing I and Br in Inorganic Perovskites: Atomistic Insights from Reactive Molecular Dynamics Simulations.

All-inorganic halide perovskites have received a great deal of attention as attractive alternatives to overcome the stability issues of hybrid halide perovskites that are commonly associated with organic cations. To find a compromise between the optoelectronic properties of CsPbI3 and CsPbBr3, perovskites with CsPb(BrxI1-x)3 mixed compositions are commonly used. An additional benefit is that without sacrificing the optoelectronic properties for applications such as solar cells or light-emitting diodes, small amounts of Br in CsPbI3 can prevent the inorganic perovskite from degrading to a photo-inactive non-perovskite yellow phase. Despite indications that strain in the perovskite lattice plays a role in the stabilization of the material, a full understanding of such strain is lacking. Here, we develop a reactive force field (ReaxFF) for perovskites starting from our previous work for CsPbI3, and we extend this force field to CsPbBr3 and mixed CsPb(BrxI1-x)3 compounds. This force field is used in large-scale molecular dynamics simulations to study perovskite phase transitions and the internal ion dynamics associated with the phase transitions. We find that an increase of the Br content lowers the temperature at which the perovskite reaches a cubic structure. Specifically, by substituting Br for I, the smaller ionic radius of Br induces a strain in the lattice that changes the internal dynamics of the octahedra. Importantly, this effect propagates through the perovskite lattice ranging up to distances of 2 nm, explaining why small concentrations of Br in CsPb(BrxI1-x)3 (x ≤ 1/4) have a significant impact on the phase stability of mixed halide perovskites.

Development and validation of a general-purpose ReaxFF reactive force field for earth material modeling.

ReaxFF reactive force field bridges the gap between nonreactive molecular simulations and quantum mechanical calculations and has been widely applied during the past two decades. However, its application to earth materials, especially those under high T-P conditions relevant to Earth's interior, is still limited due to the lack of available parameters. Here, we present the development and validation of a ReaxFF force field containing several of the most common elements in Earth's crust, i.e., Si/Al/O/H/Na/K. The force field was trained against a large data set obtained from density functional theory (DFT) calculations, including charges, bond/angle distortion curves, equation of states, ion migration energy profiles, and condensation reaction energies. Different coordination environments were considered in the training set. The fitting results showed that the current force field can well reproduce the DFT data (the Pearson correlation coefficient, Rp, is 0.95). We validated the force field on mineral-water interfaces, hydrous melts/supercritical geofluids, and bulk crystals. It was found that the current force field performed excellently in predicting the structural, thermodynamic, and transport properties of various systems (Rp = 0.95). Moreover, possible applications and future development have been discussed. The results obtained in this study suggest that the current force field holds good promise to model a wide range of processes and thus open opportunities to advance the application of ReaxFF in earth material modeling.

Watching (De)Intercalation of 2D Metals in Epitaxial Graphene: Insight into the Role of Defects.

Intercalation forms heterostructures, and over 25 elements and compounds are intercalated into graphene, but the mechanism for this process is not well understood. Here, the de-intercalation of 2D Ag and Ga metals sandwiched between bilayer graphene and SiC are followed using photoemission electron microscopy (PEEM) and atomistic-scale reactive molecular dynamics simulations. By PEEM, de-intercalation "windows" (or defects) are observed in both systems, but the processes follow distinctly different dynamics. Reversible de- and re-intercalation of Ag is observed through a circular defect where the intercalation velocity front is 0.5 nm s-1 ± 0.2 nm s.-1 In contrast, the de-intercalation of Ga is irreversible with faster kinetics that are influenced by the non-circular shape of the defect. Molecular dynamics simulations support these pronounced differences and complexities between the two Ag and Ga systems. In the de-intercalating Ga model, Ga atoms first pile up between graphene layers until ultimately moving to the graphene surface. The simulations, supported by density functional theory, indicate that the Ga atoms exhibit larger binding strength to graphene, which agrees with the faster and irreversible diffusion kinetics observed. Thus, both the thermophysical properties of the metal intercalant and its interaction with defective graphene play a key role in intercalation.

Evolution of Glassy Carbon Derived from Pyrolysis of Furan Resin.

Glassy carbon (GC) material derived from pyrolyzed furan resin was modeled by using reactive molecular dynamics (MD) simulations. The MD polymerization simulation protocols to cure the furan resin precursor material are validated via comparison of the predicted density and Young's modulus with experimental values. The MD pyrolysis simulations protocols to pyrolyze the furan resin precursor is validated by comparison of calculated density, Young's modulus, carbon content, sp2 carbon content, the in-plane crystallite size, out-of-plane crystallite stacking height, and interplanar crystallite spacing with experimental results from the literature for furan resin derived GC. The modeling methodology established in this work can provide a powerful tool for the modeling-driven design of next-generation carbon-carbon composite precursor chemistries for thermal protection systems and other high-temperature applications.

Effect of Fe-O ReaxFF on Liquid Iron Oxide Properties Derived from Reactive Molecular Dynamics.

As iron powder nowadays attracts research attention as a carbon-free, circular energy carrier, molecular dynamics (MD) simulations can be used to better understand the mechanisms of liquid iron oxidation at elevated temperatures. However, prudence must be practiced in the selection of a reactive force field. This work investigates the influence of currently available reactive force fields (ReaxFFs) on a number of properties of the liquid iron-oxygen (Fe-O) system derived (or resulting) from MD simulations. Liquid Fe-O systems are considered over a range of oxidation degrees ZO, which represents the molar ratio of O/(O + Fe), with 0 < ZO < 0.6 and at a constant temperature of 2000 K, which is representative of the combustion temperature of micrometric iron particles burning in air. The investigated properties include the minimum energy path, system structure, (im)miscibility, transport properties, and the mass and thermal accommodation coefficients. The properties are compared to experimental values and thermodynamic calculation results if available. Results show that there are significant differences in the properties obtained with MD using the various ReaxFF parameter sets. Based on the available experimental data and equilibrium calculation results, an improved ReaxFF is required to better capture the properties of a liquid Fe-O system.

Correction: Self-limiting stoichiometry in SnSe thin films.

Correction for 'Self-limiting stoichiometry in SnSe thin films' by Jonathan R. Chin et al., Nanoscale, 2023, 15, 9973-9984, https://doi.org/10.1039/D3NR00645J.

Step engineering for nucleation and domain orientation control in WSe2 epitaxy on c-plane sapphire.

Epitaxial growth of two-dimensional transition metal dichalcogenides on sapphire has emerged as a promising route to wafer-scale single-crystal films. Steps on the sapphire act as sites for transition metal dichalcogenide nucleation and can impart a preferred domain orientation, resulting in a substantial reduction in mirror twins. Here we demonstrate control of both the nucleation site and unidirectional growth direction of WSe2 on c-plane sapphire by metal-organic chemical vapour deposition. The unidirectional orientation is found to be intimately tied to growth conditions via changes in the sapphire surface chemistry that control the step edge location of WSe2 nucleation, imparting either a 0° or 60° orientation relative to the underlying sapphire lattice. The results provide insight into the role of surface chemistry on transition metal dichalcogenide nucleation and domain alignment and demonstrate the ability to engineer domain orientation over wafer-scale substrates.

Aqueous Stability of Metal-Organic Frameworks Using ReaxFF-Based Metadynamics Simulations.

Aqueous stability is a critical property for the application of metal-organic framework (MOF) materials in humid conditions. The sampling of the free energy surface for a water reaction is challenging due to a lack of a reactive force field. Here, we developed a ReaxFF force field for simulating the reaction of zeolitic imidazole frameworks (ZIFs) with water. We carried out metadynamics simulations based on ReaxFF to study the reaction of water with a few different types of MOFs. We also conducted an experimental water immersion test and characterized the XRD, TG, and gas adsorption properties of the MOFs before and after the immersion test. By considering the energy barrier for a hydrolysis reaction, the simulation results are in good agreement with the experiments. MOFs with open structures and large pores are found to be unstable in metadynamics simulations, where the water molecule can attack or bond with the metallic node relatively easily. In contrast, it is more difficult for water to attack the Zn atom in the ZnN4 tetrahedral structure of ZIFs. We also found that ZIFs with the -NO2 functional groups have higher water stability. Discrepancies between the metadynamics simulation and gas adsorption experiments have been accounted for from the phase/crystallinity change of the structure reflected in the X-ray diffraction and thermogravimetry analysis of the MOF samples.

A ReaxFF-based molecular dynamics study of the destruction of PFAS due to ultrasound.

This work uses a computational approach to provide a mechanistic explanation for the experimentally observed destruction of per- and polyfluoroalkyl substances (PFAS) in water due to ultrasound. The PFAS compounds have caused a strong public and regulatory response due to their ubiquitous presence in the environment and toxicity to humans. In this research, ReaxFF -based Molecular Dynamics simulation under several temperatures ranging from 373 K to 5,000 K and different environments such as water vapor, O2, N2, and air were performed to understand the mechanism of PFAS destruction. The simulation results showed greater than 98% PFAS degradation was observed within 8 ns under a temperature of 5,000 K in a water vapor phase, replicating the observed micro/nano bubbles implosion and PFAS destruction during the application of ultrasound. Additionally, the manuscript discusses the reaction pathways and how PFAS degradation evolves providing a mechanistic basis for the destruction of PFAS in water due to ultrasound. The simulation showed that small chain molecules C1 and C2 fluoro-radical products are the most dominant species over the simulated period and are the impediment to an efficient degradation of PFAS. Furthermore, this research confirms the empirical findings observations that the mineralization of PFAS molecules occurs without the generation of byproducts. These findings highlight the potential of virtual experiments in complementing laboratory experiments and theoretical projections to enhance the understanding of PFAS mineralization during the application of ultrasound.

Joint Theoretical and Experimental Study of Stress Graphitization in Aligned Carbon Nanotube/Carbon Matrix Composites.

Stress graphitization is a unique phenomenon at the carbon nanotube (CNT)-matrix interfaces in CNT/carbon matrix (CNT/C) composites. A lack of fundamental atomistic understanding of its evolution mechanisms and a gap between the theoretical and experimental research have hindered the pursuit of utilizing this phenomenon for producing ultrahigh-performance CNT/C composites. Here, we performed reactive molecular dynamics simulations along with an experimental study to explore stress graphitization mechanisms of a CNT/polyacrylonitrile (PAN)-based carbon matrix composite. Different CNT contents in the composite were considered, while the nanotube alignment was controlled in one direction in the simulations. We observe that the system with a higher CNT content exhibits higher localized stress concentration in the periphery of CNTs, causing alignment of the nitrile groups in the PAN matrix along the CNTs, which subsequently results in preferential dehydrogenation and clustering of carbon rings and eventually graphitization of the PAN matrix when carbonized at 1500 K. These simulation results have been validated by experimentally produced CNT/PAN-based carbon matrix composite films, with transmission electron microscopy images showing the formation of additional graphitic layers converted by the PAN matrix around CNTs, where 82 and 144% improvements of the tensile strength and Young's modulus are achieved, respectively. The presented atomistic details of stress graphitization can provide guidance for further optimizing CNT-matrix interfaces in a more predictive and controllable way for the development of novel CNT/C composites with high performance.

Role of Bilayer Graphene Microstructure on the Nucleation of WSe2 Overlayers.

Over the past few years, graphene grown by chemical vapor deposition (CVD) has gained prominence as a template to grow transition metal dichalcogenide (TMD) overlayers. The resulting two-dimensional (2D) TMD/graphene vertical heterostructures are attractive for optoelectronic and energy applications. However, the effects of the microstructural heterogeneities of graphene grown by CVD on the growth of the TMD overlayers are relatively unknown. Here, we present a detailed investigation of how the stacking order and twist angle of CVD graphene influence the nucleation of WSe2 triangular crystals. Through the combination of experiments and theory, we correlate the presence of interlayer dislocations in bilayer graphene with how WSe2 nucleates, in agreement with the observation of a higher nucleation density of WSe2 on top of Bernal-stacked bilayer graphene versus twisted bilayer graphene. Scanning/transmission electron microscopy (S/TEM) data show that interlayer dislocations are present only in Bernal-stacked bilayer graphene but not in twisted bilayer graphene. Atomistic ReaxFF reactive force field molecular dynamics simulations reveal that strain relaxation promotes the formation of these interlayer dislocations with localized buckling in Bernal-stacked bilayer graphene, whereas the strain becomes distributed in twisted bilayer graphene. Furthermore, these localized buckles in graphene are predicted to serve as thermodynamically favorable sites for binding WSex molecules, leading to the higher nucleation density of WSe2 on Bernal-stacked graphene. Overall, this study explores synthesis-structure correlations in the WSe2/graphene vertical heterostructure system toward the site-selective synthesis of TMDs by controlling the structural attributes of the graphene substrate.

Self-limiting stoichiometry in SnSe thin films.

Unique functionalities can arise when 2D materials are scaled down near the monolayer limit. However, in 2D materials with strong van der Waals bonds between layers, such as SnSe, maintaining stoichiometry while limiting vertical growth is difficult. Here, we describe how self-limiting stoichiometry can promote the growth of SnSe thin films deposited by molecular beam epitaxy. The Pnma phase of SnSe was stabilized over a broad range of Sn : Se flux ratios from 1 : 1 to 1 : 5. Changing the flux ratio does not affect the film stoichiometry, but influences the predominant crystallographic orientation. ReaxFF molecular dynamics (MD) simulation demonstrates that, while a mixture of Sn/Se stoichiometries forms initially, SnSe stabilizes as the cluster size evolves. The MD results further show that the excess selenium coalesces into Se clusters that weakly interact with the surface of the SnSe particles, leading to the limited stoichiometric change. Raman spectroscopy corroborates this model showing the initial formation of SnSe2 transitioning into SnSe as experimental film growth progresses. Transmission electron microscopy measurements taken on films deposited with growth rates above 0.25 Å s-1 show a thin layer of SnSe2 that disrupts the crystallographic orientation of the SnSe films. Therefore, using the conditions for self-limiting SnSe growth while avoiding the formation of SnSe2 was found to increase the lateral scale of the SnSe layers. Overall, self-limiting stoichiometry provides a promising avenue for maintaining growth of large lateral-scale SnSe for device fabrication.

Effect of Electrode/Electrolyte Coupling on Birnessite (δ-MnO2) Mechanical Response and Degradation.

Understanding the deformation of energy storage electrodes at a local scale and its correlation to electrochemical performance is crucial for designing effective electrode architectures. In this work, the effect of electrolyte cation and electrode morphology on birnessite (δ-MnO2) deformation during charge storage in aqueous electrolytes was investigated using a mechanical cyclic voltammetry approach via operando atomic force microscopy (AFM) and molecular dynamics (MD) simulation. In both K2SO4 and Li2SO4 electrolytes, the δ-MnO2 host electrode underwent expansion during cation intercalation, but with different potential dependencies. When intercalating Li+, the δ-MnO2 electrode presents a nonlinear correlation between electrode deformation and electrode height, which is morphologically dependent. These results suggest that the stronger cation-birnessite interaction is the reason for higher local stress heterogeneity when cycling in Li2SO4 electrolyte, which might be the origin of the pronounced electrode degradation in this electrolyte.