Force Field Molecular Dynamics Research Articles

Formation mechanism of soot in pyrolysis of 2-methylfuran under high temperature based on ReaxFF molecular dynamics simulation

In this study, the detailed mechanism of soot formation under high temperature pyrolysis of 2-methylfuran (2-MF) has been investigated by using Reactive force field molecular dynamics (ReaxFF MD) simulation. The MD analysis shows that 2-MF undergoes ring cleavage and the removal of CO/HCO/CH2CO/CH3CO, which results in the production of the C2-C4 species, promoting the formation of the initial ring molecules. The clustering of hydrocarbons by radical-chain reaction (CHRCR) mechanism plays a significant role in the mass growth of both polycyclic aromatic hydrocarbons (PAHs) and initial soot particles. The main contributors to this process are C2H2 and resonance-stabilized free radicals of C3 and C4. The H-abstraction-C2H2-addition (HACA) mechanism is important for the formation of surface active sites for PAHs and initial soot to some extent. In addition, the soot formation capacity of 2,5-dimethylfuran (25DMF) and 2-MF are compared. Under the same simulation conditions, 25DMF exhibits a higher capacity to form soot. Compared with 2-MF, 25DMF pyrolysis forms more ring-containing species at the initial stage, particularly cyclopentadiene and its derivatives. These compounds have the ability to promote the formation of PAHs, thus providing further support to the experimental-based theory.

Evaluation of the synergistic effect of platinum-supported graphene materials on methylcyclohexane decomposition via flow reactor experiments and reactive force-field molecular dynamics simulations

Hydrogen technology is a viable alternative to carbon-based energy sources. However, the widespread use of hydrogen energy is limited by its low volumetric energy density, complex supply chain, and difficulties related to hydrogen storage. This study investigates the influence of Pt-supported graphene additives on hydrogen formation and decomposition of methylcyclohexane (MCH), which is a potential hydrogen carrier, by conducting high-pressure liquid flow reactor experiments and reactive force-field molecular dynamics simulations. This investigation represents a notable improvement in the MCH decomposition and hydrogen generation efficiencies through enhanced catalytic dehydrogenation facilitated by Pt-decorated functionalized graphene sheets (Pt@FGSs). Experimental results indicate that under fixed reaction conditions, the bicomposite structure of the Pt@FGSs at a loading concentration of 50 ppmw reduces the dehydrogenation energy and increases the conversion rate by up to 45%. The yields of products such as hydrogen and low-carbon species are also significantly improved. Notably, hydrogen formation is enhanced by a factor of approximately 2, demonstrating the effectiveness of Pt@FGSs in facilitating fuel decomposition and promoting hydrogen production. In addition, reactive force-field molecular dynamics simulations elucidate possible enhancement mechanisms, in which Pt nanoparticles attach to FGSs and catalyze the dehydrogenation of MCH and its derivatives. The production of a higher amount of the produced hydrogen is evidenced by the desorption of H atoms attached to the Pt surface. This study provides valuable insights that can accelerate the transition towards sustainable and effective decarbonization strategies using MCH as a hydrogen carrier.

Methanol-assisted NO oxidation under an oxygen atmosphere for efficient denitration: Experiments and ReaxFF-MD simulations

The development of selective catalytic reduction technologies for controlling nitrogen oxide (NOx) emissions in flue gas is hampered by high equipment and catalyst costs. In this study, a catalyst-free and efficient denitration process using methanol and oxygen as reactants was developed. Various gas atmospheres with differing concentrations were investigated to remove NO without catalysts. The addition of methanol significantly enhanced NO removal efficiency, reaching 94.6 % at 550 °C, with 55.1 % of NO converted to NO2, which can be absorbed by downstream alkali solutions. Reactive force field molecular dynamics (ReaxFF-MD) simulations were employed to analyze the atomic level NO oxidation mechanism in the CH3OH/NO/O2/H2O homogeneous reaction system. The simulation revealed the generation pathway of three key oxidizing intermediates (OH, HO2, and H2O2) and their roles in NO oxidation. This study offers critical insights into developing a cost-effective denitration process, highlighting the potential for improved NOx emission control.

Soot formation and laminar combustion characteristics of anisole: ReaxFF MD simulation and kinetic analysis

The application of biomass energy is one of the important ways to achieve carbon neutrality and deal with global warming. The study on the combustion mechanism of anisole, an oxygen-containing fuel, is helpful for biofuel large-scale application. In this study, the soot formation and laminar combustion characteristics of anisole were analyzed by reactive force field molecular dynamics (ReaxFF MD) and kinetic simulation, respectively. ReaxFF MD simulation studies had shown that soot formation of anisole combustion occurred in three stages, stage 1 (0–1 ns), stage 2 (1–2.5 ns), stage 3 (2.5–6 ns). The three stages represented the pyrolysis of the fuel, the developmental stage of the soot, and the graphitization stage of the soot, respectively. During the combustion of anisole, primary mechanisms for the soot formation were as follows: H-abstraction-C2H2-addition, carbon-addition-hydrogen-addition, internal ring formation and long carbon chain link. The formation of soot graphitization exhibited different morphologically behaviors: from flakes to onions to spheres with fewer branched chains. From the study of the laminar combustion characteristics of anisole, it can be found that the laminar burning velocities increased along with the increase of temperature, while the opposite trend was shown along with the increase of pressure. The sensitivity coefficient of naphthalene, the main soot precursor, revealed that the main promotional reactions for soot formation were R5 (O2 + H < = > O + OH), R36 (CO + OH < = > CO2 + H).

Effects of oxidizer concentration and abrasive type on interfacial bonding and material removal in 4H-SiC polishing processes.

Determination of chemical effects involved in material removal during the polishing process of 4H-SiC has been a challenge. In this study, the polishing processes of 4H-SiC under the action of diamond and SiO2 abrasive in different concentrations of H2O2 solutions are investigated by reactive force field molecular dynamics simulations. It is found that 4H-SiC can be oxidized by H2O2 solution at the atomic scale, but the chemical reaction alone does not lead to material removal. An increase in the concentration of H2O2 solution and the mechanical action of abrasives can promote the oxidation of 4H-SiC. Since the mechanical removal dominates material removal when polishing 4H-SiC with diamond abrasive, there is no clear pattern in the effect of H2O2 solution concentration on material removal. Nevertheless, the removal of atoms associated with chemical bonds dominates material removal when polishing 4H-SiC with SiO2 abrasive. Therefore, the damage and atomic removal of 4H-SiC are lower. Since the H2O2 solution can increase the total number of bonds between 4H-SiC and SiO2 abrasive, an increase in the concentration of H2O2 solution can improve the material removal rate. These findings can provide guidance for the 4H-SiC polishing process in terms of abrasive and oxidizer selection.

Unraveling the reaction mechanism of alkali-activated materials through multi-scale modeling

As an environmentally friendly alternative to cement-based materials, alkali-activated materials (AAM) have attracted much attention due to their significant ability to reduce greenhouse gas emissions and effectively utilize industrial waste. Three Si-Al monomers ([SiO2(OH)2]2-, [SiO(OH)3]-, and [Al(OH)4]-) serve as the fundamental building blocks for the formation of AAM gels. Simulating their polycondensation reactions (PR) among these monomers is of paramount importance but faces a delicate balance between precision and efficiency. To unravel the PR mechanisms, we have integrated reactive force field molecular dynamics (MD) simulations with first-principles calculations based on density functional theory. Our 100ps MD simulations reveal that Al monomers exhibit faster reaction rates and lead to the formation of Si-Al oligomers with diverse structures. Subsequent first-principles calculations on transition state models derived from MD results uncover that PR pathways involving Al monomers possess lower energy barriers, which are correlated with changes in chemical bond strength arising from electronic orbital transitions. Our study, for the first time, establishes an intrinsic link among five hierarchical levels: electronic orbital structure, chemical bond strength, reaction energy barrier, reaction rate, and reaction scale. This provides invaluable theoretical guidance for designing energy-efficient and low-barrier reaction pathways for AAM gel formation.

Computational Multiscale Study of the Interaction Between the PDMS Polymer and Sunscreen-Related Pollutant Molecules

Sunscreen molecules play a critical role in protecting skin from ultraviolet radiation, yet their efficient detection and separation pose challenges in environmental and analytical contexts. In this work, we employ a multilevel modeling approach to investigate the molecular interactions between representative sunscreen molecules and the polydimethylsiloxane (PDMS) polymer, a material widely recognized for its sorbent properties. Our goal is to explore how these interactions can be fine-tuned to facilitate the effective separation of sunscreen molecules in portable membrane inlet mass spectrometry (MIMS) systems, potentially leading to the development of new membrane materials. Using a combination of advanced computational techniques—force field molecular dynamics simulations, semiempirical GFN2-xTB, and density functional theory calculations—we assess the interaction strength and noncovalent interactions of sunscreen molecules, namely oxybenzone, naphthalene, benzo[a]anthracene, avobenzone, and 1,3,5-trichlorobenzene, with PDMS. Additionally, the effect of temperature on the interaction dynamics is evaluated, with the aim of extending the sorbent capacities of PDMS beyond light polar molecules to larger, polar sunscreen compounds. This study provides critical insights into the molecular-level interactions that may guide the design of novel membrane materials for efficient molecular separation.

Behavior of Trapped Molecules in Lantern-Like Carcerand Superphanes.

Superphanes are a group of organic molecules from the cyclophane family. They are characterized by the presence of two parallel benzene rings joined together by six bridges. If these bridges are sufficiently long, the superphane cavity can be large enough to trap small molecules or ions. Using ab initio (time scale of 80 ps) and classical (up to 200 ns) molecular dynamics (MD) methods, we study the behavior of five fundamental molecules (M = H2O, NH3, HF, HCN, MeOH) encapsulated inside the experimentally reported lantern-like superphane and its two derivatives featuring slightly modified side bridges. The main focus is studying the dynamics of hydrogen bonds between the trapped M molecule and the imino nitrogen atoms of the side chains of the host superphane. The length of the N···H hydrogen bond increases in the following order: HF < HCN < H2O < MeOH < NH3. The mobility of the trapped molecule and its preferred position inside the superphane cage depend not only on the type of this molecule but also largely on the in/out conformational arrangement of the imino nitrogens in the side chains of the superphane. Their inward-pointing positions allow the formation of strong N···H hydrogen bonds. For this reason, these nitrogens are the preferred sites of interaction. The mobility of the molecules and their residence times on each side of the superphane have been explained by referring to the symmetry and conformation of the given superphane cage. All force field MD simulations have shown that the encapsulated molecule remained inside the superphane cage for 200 ns without any escape event to the outside. Moreover, our simulations based on some endohedral complexes in the water box also showed no exchange event. Thus, the superphanes we study are true carcerand molecules. We attribute this property to the hydrophobic side chains and their pinwheel arrangement, which makes the side walls of the studied superphanes fairly impenetrable to small molecules.

Insight into the mechanism of H2O promoted CaCO3 decomposition in CO2 atmosphere

Calcium looping is one of the most promising CO2 capture technology. The flus gas during the calcination stage of the calcium looping contains both CO2 and H2O. However, the effect of H2O on the decomposition of carbonation in the CO2 atmosphere remains inconclusive. This study employed the Reactive Force Field molecular dynamics (ReaxFF-MD) simulations to investigate the influence of H2O on the decomposition of calcium carbonate in a CO2 atmosphere. The TGA experiments demonstrated that H2O increases the decomposition rate of calcium carbonate and also reduces the reaction temperature. Subsequently, the effects of varying CO2 and H2O concentrations on the decomposition of calcium carbonate were examined using ReaxFF-MD simulations. The simulation results for calcium carbonate decomposition, with the addition of CO2 and H2O, aligned with the experimental trends, verifying the reliability of the models. By tracking and labeling carbon, oxygen and hydrogen atom sources in the simulation, the decomposition, carbonation and hydrolysis reaction network for the CaCO3 decomposition in CO2 atmosphere was systematically constructed. Analysis of the chemical reactions and atomic distribution indicated that H2O primarily facilitates calcium carbonate decomposition by generating HCO3− through surface hydrolysis, which reduces the activation energy of the reaction. Moreover, the hydroxyl groups formed by hydrolysis compete with atmospheric CO2 for active sites on CaO, further inhibiting the carbonation reaction and increasing the calcination rate.

Propensity of hydroxide and hydronium ions for the air-water and graphene-water interfaces from abinitio and force field simulations.

Understanding acids and bases at interfaces is relevant for a range of applications from environmental chemistry to energy storage. We present combined abinitio and force-field molecular dynamics simulations of hydrochloric acid and sodium hydroxide highly concentrated electrolytes at the interface with air and graphene. In agreement with surface tension measurements at the air-water interface, we find that HCl presents an ionic surface excess, while NaOH displays an ionic surface depletion, for both interfaces. We further show that graphene becomes less hydrophilic as the water ions concentration increases, with a transition to being hydrophobic for highly basic solutions. For HCl, we observe that hydronium adsorbs to both interfaces and orients strongly toward the water phase, due to the hydrogen bonding behavior of hydronium ions, which donate three hydrogen bonds to bulk water molecules when adsorbed at the interface. For NaOH, we observe density peaks of strongly oriented hydroxide ions at the interface with air and graphene. To extrapolate our results from concentrated electrolytes to dilute solutions, we perform single ion-pair abinitio simulations, as well as develop force-field parameters for ions and graphene that reproduce the density profiles at high concentrations. We find the behavior of hydronium ions to be rather independent of concentration. For NaOH electrolytes, the force-field simulations of dilute NaOH solutions suggest no hydroxide adsorption but some adsorption at high concentrations. For both interfaces, we predict that the surface potential is positive for HCl and close to neutral for NaOH.

ReaxFF molecular dynamics study of N-containing PAHs formation in the pyrolysis of C2H4/NH3 mixtures

The reactive force field molecular dynamics (ReaxFF MD) simulations are performed to depict the whole process including fuel pyrolysis, the formation and growth of PAHs/NPAHs and soot formation in the pyrolysis of C2H4 and C2H4/NH3 mixtures. NH3 doping increases the concentration of H radicals through the decomposition of NH3. These H radicals then promote the consumption of C2H4 by participating in H-abstraction reactions. The formation of C-N species (mainly HCN, H2CN, C2N, CH3CN, NCCN, and HC3N) removes the C atoms participating in the formation of PAHs and soot, thus inhibiting the formation of soot. And such inhibitory effect is strengthened with increasing temperature due to the promoted formation of C-N species. Most importantly, the structure, formation and evolution paths of N-containing PAHs (NPAHs) are identified based on the experimental and simulation results for the first time, revealing that N atoms in the NPAHs are almost always present in the carbon chains attached to the aromatic rings while barely enter the rings to form heterocyclic structure. The simulations further reveal that when the temperature is less than 2500 K, the first N-containing aromatic ring is formed through the reaction of phenyl with small C-N species (such as HCN and CN radicals), followed by the increase of new rings primarily via the HACA mechanism. At temperatures greater than 2500 K, the formation and growth of NPAHs are dominated by the continuous attachment of N-containing carbon chains and cyclic polycondensation-cyclization reactions. The identification of new C-N species especially NPAHs would help improve the kinetic mechanisms for ammonia blending combustion.

Shock Hugoniot calculations using on-the-fly machine learned force fields with ab initio accuracy

We present a framework for computing the shock Hugoniot using on-the-fly machine learned force field (MLFF) molecular dynamics simulations. In particular, we employ an MLFF model based on the kernel method and Bayesian linear regression to compute the free energy, atomic forces, and pressure, in conjunction with a linear regression model between the internal and free energies to compute the internal energy, with all training data generated from Kohn–Sham density functional theory (DFT). We verify the accuracy of the formalism by comparing the Hugoniot for carbon with recent Kohn–Sham DFT results in the literature. In so doing, we demonstrate that Kohn–Sham calculations for the Hugoniot can be accelerated by up to two orders of magnitude, while retaining ab initio accuracy. We apply this framework to calculate the Hugoniots of 14 materials in the FPEOS database, comprising 9 single elements and 5 compounds, between temperatures of 10 kK and 2 MK. We find good agreement with first principles results in the literature while providing tighter error bars. In addition, we confirm that the inter-element interaction in compounds decreases with temperature.

Pyrolysis mechanism of 1,1,1,2-tetrafluoroethane and 1,1,1,2-tetrafluoroethane/carbon dioxide as working fluids for transcritical power cycles: Insights from reactive force field molecular dynamics and density functional theory studies

Carbon dioxide-based mixtures in transcritical power cycle systems can enhance thermodynamic performance but may pose risks of thermal decomposition, potentially compromising system performance and safety. This study investigates the pyrolysis mechanism of 1,1,1,2-tetrafluoroethane (R134a)/carbon dioxide (CO₂), a typical CO₂-based mixture, using reactive force field molecular dynamics (ReaxFF-MD) simulations and density functional theory (DFT). ReaxFF-MD simulations are conducted at pressures ranging from 4 to 12 MPa and temperatures between 1800 K and 3200 K for various fluid compositions, including pure R134a and R134a/CO₂ mixtures at mole ratios of 0.7/0.3, 0.5/0.5, and 0.3/0.7. The effects of temperature, pressure, and composition on the thermal decomposition of both pure R134a and R134a/CO₂ mixtures are examined, with particular focus on behavior at 8 MPa. In the thermal decomposition of R134a/CO₂ mixtures, CO₂ inhibits the formation of F radicals and reduces their concentration through chemical reactions, thereby suppressing R134a decomposition. Pure R134a decomposes into primary products such as hydrogen fluoride (HF), fluorine (F), tetrafluoroethylene (C2HF4), trifluoromethyl radicals (CF3), and diatomic carbon (C2). The addition of CO2 results in the formation of additional products, including carbonyl fluoride (COF), oxygen (O), hydroxyl (HO), and formyl radicals (CHO). The decomposition pathways involve two reaction types: self-decomposition reactions dominate initially, while extraction reactions become more prominent later. Using the DFT approach, reaction energy barriers are analyzed to corroborate the ReaxFF-MD simulation findings. Moreover, the apparent activation energies for these reactions are quantified using first-order kinetics based on the Arrhenius equation, indicating that the thermal decomposition of R134a/CO2 mixtures is more challenging than that of pure R134a.

Study of the proton transfer during acidification of sodium salicylate based on ReaxFF molecular dynamics simulation

Salicylic acid(SA) is known for its pain-relieving and fever-reducing abilities and has a very broad range of applications, being an important ingredient in a wide variety of products such as pharmaceuticals, skin care products, agrochemicals, dyes, colorants, preservatives, and more. SA is mainly synthesized by the Kolbe-Schmitt method in industrial production, but there is still no standardized description of the mechanism of this reaction. The Kolbe-Schmitt reaction mechanism is divided into three steps, and the reaction mechanism of the first two steps has been fully investigated, while the reaction mechanism of Sodium salicylate (SS) acidification, as the last step in the synthesis of SA by the Kolbe-Schmitt process, has not been investigated, so we used the Reactive force-field molecular dynamics simulation (ReaxFF MD) method to simulate and reveal the reaction mechanism of the mixed solution of SS and sulfuric acid, followed by an orthogonal design to explore the effects of different factors on the yield of SA. Through the investigation, it was found that the reaction of SS with sulfuric acid mixed solution was divided into the following four stages in total: hydration reaction, proton transfer reaction, association reaction and dissociation reaction, respectively. It is concluded that the SA yield in SS acidification reaction is affected by the factors in the following order: concentration > pressure > time > temperature, where concentration and pressure significantly affect the SA yield. It is hoped that the present study can supplement the relevant understanding of the reaction mechanism of the Kolbe-Schmitt process, and at the same time have some practical significance and application value for the improvement and optimization of the synthetic SA process.

Analysis of the nanostructure evolution of soot in n-heptane/iso-octane with 2,5-dimethylfuran addition: A combined experimental study and ReaxFF MD simulations

The soot formation of n-heptane/iso-octane doped 2,5-dimethylfuran (DMF) with different ratios was experimentally investigated through laminar diffusion flame and numerically simulated by using the pyrolysis simulations method of reactive force field molecular dynamics (ReaxFF MD). The results showed that the laminar diffusion flame height of n-heptane/iso-octane increased with increasing DMF doping ratio. At a consistent sampling height, the primary soot particle sampling numbers collected were first decreasing and then increasing, and the size of the primary soot particle was first increasing and then decreasing accompanied by the DMF doping ratio increasing. Furthermore, the transmission electron microscope (TEM) analysis provided that DMF initially inhibited and subsequently promoted the primary soot particle growth in the n-heptane/iso-octane flame. The core-shell ratio increased and then decreased with the increase of the DMF doping ratio, which indicated that the maturity of soot decreased and then increased. In n-heptane/iso-octane doped with DMF ReaxFF MD pyrolysis simulation, it was divided into three stages 0–0.5 ns (the first stage), 0.5–3 ns (the second stage), and 3–4.5 ns (the third stage). Fuel decomposed in the first stage and reacted violently in the second stage. The soot precursors continued to react, molecule size kept to increase, and the polycyclic aromatic hydrocarbons (PAHs) continued to grow. In the third stage, the carbon number of the largest molecules were slowly increasing, and the development of soot entered mature stage, where the H/C ratio was slowly decreasing. Through ReaxFF MD simulations, it was found that the maturity of soot exhibited decreasing and then increasing trend with the increase of DMF doping ratio. The graphene-like structures were mainly concentrated around the H/C ratio of 0.297 region.

The dissolution of metal carbonate precipitation under the external electric and magnetic fields: reactive force field molecular dynamics simulation

Abstract The dissolution of metal carbonates holds a pivotal role in diverse industrial processes, environmental occurrences, and geological formations. Grasping the fundamental mechanisms underlying these processes is imperative for enhancing industrial applications and mitigating environmental impacts. Herein, we undertake a thorough investigation employing reactive forcefieldmolecular dynamics simulations to delve into the dissolution process of metal carbonates. These simulations afford profound insights into the mechanisms and kinetics governing the process across various conditions, encompassing temperature, acidity, and external electric and magnetic fields. Although temperature itself exerts a limited influence, the study reveals a synergistic enhancement of metal carbonate dissolution kinetics when temperature is combined with static electric and magnetic fields. Our revelations offer enlightening perspectives on the intricate interplay of factors shaping dissolution processes, laying the foundation for future inquiries in this domain.

Thermal stability of MDM and oxidative decomposition mechanism under the condition of air infiltration: A combined experimental, ReaxFF-MD and DFT study

When siloxanes are used as the working fluids of organic Rankine cycle systems, there is a possibility of air infiltration due to the large vacuum present in the condenser. To address this issue, experimental and simulation studies were conducted on the thermal stability and pyrolysis product characteristics of octamethyltrisiloxane (MDM) in the presence of air. The results indicated that air significantly promotes the decomposition of MDM at the temperatures above 250 °C. Air was helpful in increasing the formation of CH2O, CO, and CO2, and also enhanced polymerization of decomposition product of siloxane, leading to higher yields of MD2M, MD3M, MD4M, D3, D4, and D5. By combining reactive force field molecular dynamics (ReaxFF-MD) simulations with density functional theory (DFT) calculations, the microscopic mechanisms of MDM's oxidative decomposition by O2 in air and H2O under humid conditions were elucidated. O2 can easily combine with unsaturated Si atoms to form Si-O bonds, combine with CH3 radicals to form C-O bonds, and undergoes hydrogen extraction reactions to initiate decomposition. H2O mainly undergoes initial decomposition through CH3 radical hydrogenation and binding with unsaturated Si atoms. The generated O2H, O, and OH radicals tend to bind with Si atoms in molecules and radicals, facilitating polymerization reactions.

Unveiling Carbon Cluster Coating in Graphene CVD on MgO: Combining Machine Learning Force field and DFT Modeling.

In this study, we investigate the behavior of carbon clusters (Cn, where n ranges from 16 to 26) supported on the surface of MgO. We consider the impact of doping with common impurities (such as Si, Mn, Ca, Fe, and Al) that are typically found in ores. Our approach combines density functional theory calculations with machine learning force field molecular dynamics simulations. It is found that the C21 cluster, featuring a core-shell structure composed of three pentagons isolated by three hexagons, demonstrates exceptional stability on the MgO surface and behaves as an "enhanced binding agent" on MgO-doped surfaces. The molecular dynamics trajectories reveal that the stable C21 coating on the MgO surface exhibits less mobility compared to other sizes Cn clusters and the flexible graphene layer on MgO. Furthermore, this stability persists even at temperatures up to 1100K. The analysis of the electron localization function and potential function of Cn on MgO reveals the high localization electron density between the central carbon of the C21 ring and the MgO surface. This work proposes that the C21 island serves as a superstable and less mobile precursor coating on MgO surfaces. This explanation sheds light on the experimental defects observed in graphene products, which can be attributed to the reduced mobility of carbon islands on a substrate that remains frozen and unchanged.

Kinetic insight of multi-molecule adsorption behaviors into the anticorrosion performance of azole inhibitors: A reactive force field molecular dynamics study

Density functional theory (DFT) calculations and molecular dynamics (MD) simulations are established as powerful tools in understanding the anti-corrosion mechanism of inhibitors at the atomic scale. Despite their widespread popularity, DFT calculations typically focus on small adsorption models while the inhibition efficiency of inhibitors is determined by multi-molecule adsorption film on metal surface. Classical MD simulations neglect the formation of chemical bonding, which frequently governs the overall adsorption process. In this contribution, reactive force field (ReaxFF) MD simulations were employed to overcome these limitations and investigate the differences in inhibitory capabilities among three classic azole compounds: imidazole (IDZ), 1,2,4-triazole (TAZ), and benzotriazole (BTA) on copper. Electrochemical tests and microscopic observations revealed that BTA demonstrated superior inhibitory effect on copper corrosion compared to IDZ and TAZ. However, the widely used descriptor, adsorption energy (Eads) in DFT calculations for predicting the inhibition ability of inhibitors were very similar, failing to explain the enormous variation in inhibition effectiveness. To explain this disparity, multi-molecule adsorption kinetics based on ReaxFF simulations were conducted. The results showed that BTA consistently demonstrated faster and more frequent adsorption on copper surface compared to the other two. The significant variance in inhibitory efficiency among the three inhibitors was elucidated for the first time from the kinetic insight.

Predicting the properties of bitumen using machine learning models trained with force field atom types and molecular dynamics simulations

This study enhances the molecular analysis of bitumen by transitioning from traditional chemical descriptors, such as SARA (Saturates, Aromatics, Resins, and Asphaltenes) fractions and elemental compositions, to specific force field atom types in Molecular Dynamics (MD) models. This shift improves the precision in predicting material properties critical for bituminous material characterization. Machine Learning Models (MLMs) were developed to use these atom types as input features, inherently reflecting fundamental chemical characteristics. Trained on data from over 1,770 LAMMPS simulations of diverse bitumen types and conditions, these MLMs enable the prediction of properties like density, heat capacity, solubility parameters, and thermal expansion coefficients without the need for additional MD simulations. The models utilize 30 chemical descriptors corresponding to specific atom types in the PCFF force field, which collectively account for over 95% of the influence on these properties. By accurately predicting fundamental, thermodynamic, and kinetic properties, the use of MLMs and force field atom types allows researchers to efficiently tweak the chemical nature of organic molecules and mixtures to achieve desired properties. With near-instantaneous prediction times, these MLMs offer valuable insights for advancing bitumen research in the construction and petroleum industries, reducing the need for more intensive simulation techniques.