Energetic Calculations Research Articles

Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations

AbstractThe crystal structures of seven metal dihalide complexes with triphenylphosphine (PPh₃) and two with tribenzylphosphine (PBz₃) have been reanalyzed. The studied complexes include [FeCl₂(PPh₃)₂], [CoCl₂(PPh₃)₂], [CoBr₂(PPh₃)₂], [NiCl₂(PPh₃)₂], [NiBr₂(PPh₃)₂], [NiI₂(PPh₃)₂], [ZnCl₂(PPh₃)₂], [NiCl₂(PBz₃)₂], and [NiBr₂(PBz₃)₂]. A detailed geometric analysis revealed high isostructurality among several pairs. Ligand steric effects were assessed using cone angles and percentage surface coverage. Crystal packing is stabilized by weak C─H⋯π and C─H⋯X (X = Cl, Br, and I) interactions. Notably, [NiCl₂(PBz₃)₂] and [NiBr₂(PBz₃)₂] feature rare intramolecular C─H⋯Ni anagostic interactions. Reduced density gradient (RDG) and noncovalent interaction (NCI) plots confirmed weakly attractive C─H⋯π contacts in all complexes. Void‐volume analysis assessed the mechanical strength of the crystals, while pixel energy and energy frameworks clarified structural stability and dominant interactions. Density Functional Theory (DFT) calculations, along with QTAIM/NCIplot and NBO analyses, as well as electron density (ED) versus electrostatic potential (ESP) plots, were performed to better understand the C─H···Ni interactions and distinguish between agostic and anagostic interactions.

Electric Field-Induced Sequential Prototropic Tautomerism in Enzyme-like Nanopocket Created by Single Molecular Break Junction.

Mastering the control of external stimuli-induced chemical transformations with detailed insights into the mechanistic pathway is the key for developing efficient synthetic strategies and designing functional molecular systems. Enzymes, the most potent biological catalysts, efficiently utilize their built-in electric field to catalyze and control complex chemical reactions within the active site. Herein, we have demonstrated the interfacial electric field-induced prototropic tautomerization reaction in acylhydrazone entities by creating an enzymatic-like nanopocket within the atomically sharp gold electrodes using a mechanically controlled break junction (MCBJ) technique. In addition to that, the molecular system used here contains two coupled acylhydrazone reaction centers, hence demonstrating a cooperative stepwise electric field-induced reaction realized at the single molecular level. Furthermore, the mechanistic studies revealed a proton relay-assisted tautomerization showing the importance of external factors such as solvent in such electric field-driven reactions. Finally, single-molecule charge transport and energetics calculations of different molecular species at various applied electric fields using a polarizable continuum solvent model confirm and support our experimental findings. Thus, this study demonstrates that mimicking an enzymatic pocket using a single molecular junction's interfacial electric field as a trigger for chemical reactions can open new avenues to the field of synthetic chemistry.

Enhanced Chemical Stability of Tetramethylammonium Head Groups via Deep Eutectic Solvent: A Computational Study.

The chemical stability of tetramethylammonium (TMA) head groups, both with and without the presence of a choline chloride and ethylene glycol-based deep eutectic solvent (DES), was studied using Density Functional Theory (DFT) calculations and ab initio Molecular Dynamics (MD) simulations. DFT calculations of transition state energetics (ΔEreaction, ΔGreaction, ΔEactivation, and ΔGactivation) for key degradation mechanisms, ylide formation (YF) and nucleophilic substitution (SN2), suggested that the presence of DES enhances the stability of the TMA head groups compared to systems without DES. Ab initio MD simulations across hydration levels (HLs) 1 to 5 indicated that without DES, YF dominates at lower HLs, while SN2 does not occur. In contrast, both mechanisms are suppressed in the presence of DES. Temperature also plays a role: without DES, YF dominates at 298 K, while SN2 becomes prominent at 320 K and 350 K. With DES, both degradation mechanisms are inhibited. These findings suggest DES could improve the chemical stability of TMA head groups in anion exchange membranes.

An integrated approach combining experimental, informatics and energetic methods for solid form derisking of PF-06282999

The landscapes of observed and predicted three-dimensional crystal packing arrangements of small-molecule drug candidates can be complex. The possible appearance of a more thermodynamically stable solid form during drug development has led to the digital workflow of informatics-based risk assessments, named a Solid Form Health Check. Herein, we describe the use of a combined approach consisting of experiments, informatics together with energetic calculations in analysis of four competing polymorphs of PF-06282999, a myeloperoxidase (MPO) inhibitor with conformational flexibility and multiple plausible hydrogen bond networks. This combined approach offered a comprehensive understanding of the solid form structure, properties, and performance, ensuring robust solid form derisking and selection.

Beast DB: A Computational Electrocatalysis Database with Solvation, Grand-Canonical Applied Potential, and Beyond-DFT Reaction Energetics

Electrocatalytic reactions are key to decarbonizing the world economy, but progress in understanding electrocatalytic systems is often hindered by the diversity of conditions under which experiments are run and calculations are performed. This diversity is most often a result of experimental innovation to achieve better electrocatalyst performance, but nonetheless makes it difficult to establish clear baselines for electrocatalytic performance and to understand the fundamental factors that govern changes in performance. In order to make clear comparisons between different electrochemical configurations routine, we have constructed BEAST DB: the Beyond-DFT Electrochemistry with Accelerated and Solvated Techniques database. BEAST DB contains the most promising electrocatalysts for CO2reduction (CO2RR), the oxygen reduction reaction (ORR), the oxygen evolution reaction (OER), the hydrogen evolution reaction (HER), and nitrogen reduction reaction (NRR). For each electrocatalyst and chemistry, we have computed the adsorption energies, 𝛥Gads, and electronic properties for the most relevant catalyst facets and applied potentials. In this talk, we discuss general trends observed from this high-throughput database approach, and examine a few catalysts and chemistries in detail. Additionally, we describe our delta learning approach to learn high-fidelity reaction energetics from less expensive, lower-fidelity DFT calculations and applications of it to electrocatalytic systems. We illustrate how calculations of potential-dependent reaction energetics, as well as observables such as oxidation state and vibrational frequencies, allows for detailed comparisons to experiments such as X-ray absorption spectroscopy (XAS), Surface-enhanced infrared absorption spectroscopy (SEIRAS), and cyclic voltammetry. BEAST DB provides a wealth of information for both computationalists and experimentalists in the field of electrocatalysis, and provides a foundation for exploration of the underlying factors that govern electrocatalytic performance across a wide range of catalysts and chemistries.

First-principles insights into solute partition among various nano-phases in Al−Cu−Li−Mg alloys

First-principles energetics calculations were performed over a group of 25 candidate elements, to investigate their partition energies and behaviors among major nano-phases (δʹ-Al3Li, θʹ-Al2Cu, T1-Al6Cu4Li3 and S-Al2CuMg) in most commercial Al−Cu−Li−Mg alloys. It was revealed that principal alloying element Li cannot directly affect θʹ and S, Cu cannot directly affect δʹ, Mg cannot directly affect θʹ and δʹ but can weakly partition into T1. As for micro-alloying elements, Si is the only element that can partition into all the four nano-phases. Au can partition into δʹ, θʹ and S. Cd can partition into δʹ, T1 and S. Zr can partition into δʹ and T1. Ni substitution can weakly partition into θʹ and S. Ti, V, Zn, Ag and Mo can partition into δʹ only. Cr, Mn, Fe and Co cannot directly affect any of the four nano-phases. Almost all RE-elements can strongly partition into T1, δʹ and S, but would be expelled by θʹ. Only Sc is somehow particular to S, showing no partition preference in S. The newly obtained fundamental results could constitute a simple prototype database in support for the accelerated design of Al−Li based alloys and other related Al alloys.

Thermal analysis of aerogels and their vacuum-formed forms, their potential uses, and their effects on the environment

The main topic of the paper is to investigate the thermal examination of aerogels and their vacuumed forms, application possibilities, and environmental impact. In the paper, the thermal conductivity of homemade vacuum insulation panels was tested with different silica-based core materials. Three types of fibrous aerogel materials were used as core materials; another silica-based microporous insulation was used as a filling material. Microscopic images were taken from the core materials; furthermore, the thermal conductivities of both base materials and their vacuumed form were also tested at different mean temperatures (0, 10 and 20 °C). The results regarding the applicability of these materials as filling-core materials for vacuum insulation panels are interesting. The results showed that for microtherm and pyrogel, the thermal conductivities decreased more than 15%, while for the spaceloft and slentex it was about 8 and 2%, respectively, after evacuating the air. The paper also presents compressibility changes of the samples after vacuumization. The results were used as a basis for building energetic calculations; furthermore, the comparison of different materials from their carbon footprint point of view was also presented. These calculations depicted aerogel's very long payback time with a current market price.

A kinetic model of diffusional phase transformations in ternary line compounds and determination of diffusion coefficients: Application to the Nb–Mo–Si system

The diffusional phase transformations in inhomogeneous multicomponent systems play an important role in affecting the material properties. Ternary line compounds, which are ternary phases with components that have both large and small solid solubility, are often observed in applications. They are different from solid solutions with variable composition ratios and stoichiometric compounds with fixed composition ratios. However, the existing models cannot quantitatively characterize the diffusional phase transformations in ternary line compounds. Therefore, by introducing the state equation related to the chemical potential and mole fraction, a kinetic model of diffusional phase transformations was established for the first time to describe the mole fraction evolution and phase growth in ternary line compounds. Furthermore, a method to determine the tracer diffusion coefficients of components related to the mole fraction and crystal phase structure in ternary line compounds was proposed, and applied to the diffusion of Nb-Mo-Si ternary system composed of the MoSi2 and Nb. During the high-temperature diffusion process of Nb-MoSi2, the silicide-poor phase (Mo, Nb)5Si3 is formed, which is a typical ternary line compound. Based on the diffusion experiments and inverse calculations, the tracer diffusion coefficients of components in ternary line compound (Mo, Nb)5Si3 were experimentally obtained. Moreover, ab-initio calculations of defect energetics clarified the microscopic diffusion mechanisms in the silicide-poor phase, and explained the reason why that the diffusion coefficient of Si decreases significantly with the increase of Nb mole fraction in ternary line compound (Mo, Nb)5Si3. The research provides valuable guidance for modeling and analyzing the diffusional phase transformation of multi-component systems.

Investigation of the titanium-mediated catalytic enantioselective oxidation of aryl benzyl sulfides containing heterocyclic groups.

Our enantioselective oxidation protocol, based upon hydroperoxides in the presence of a titanium/(S,S)-hydrobenzoin catalyst, was tested for the first time with aryl benzyl sulfides containing heterocyclic moieties (2-thienyl, 2-pyridyl and benzimidazolyl), two of them being connected with the blockbuster omeprazole drug. Good yields of enantiopure sulfoxides were obtained in most cases. Two exceptions of unsatisfactory enantioselectivity in the oxidation of benzimidazolyl sulfides are reported. However, one of them was solved by crystallization of an enantio-enriched mixture. The present work was supported also by X-ray diffraction analysis of some synthesized sulfoxides and by energetic calculation of the crystal structures. The unexpected result is that the crystal structures of the racemic mixture of the two problematic benzimidazolyl sulfoxides are composed of separate enantiomers (a conglomerate), an interesting result that could be exploited in the future for the separation of the enantiomers of these sulfoxides.

Adsorption and dehydrogenation of ammonia on Ru55, Cu55 and Ru@Cu54 nanoclusters: role of single atom alloy catalyst.

Hydrogen production by the catalytic decomposition of ammonia (NH3) is an important process for several important applications, which include energy production and environment-related issues. The role of single Ru-atom substitution in a Cu55 nanocluster (NC) has been illustrated using the NH3 decomposition reaction as a model system. The structural stability of Ru@Cu54 NC has been evaluated using Ru55 and Cu55 NCs for comparison. Ru@Cu54 prefers an icosahedron structure (Ih), like Ru55 and Cu55 NCs, with almost comparable average binding energies of -5.55 eV per atom. The adsorption of NHx (x = 0-3) on different adsorption sites of the icosahedron Ru@Cu54 NC has also been studied and the corresponding adsorption energies have been estimated. The site-preference investigation suggested that NH3 prefers to adsorb vertically to the Ru@Cu54. The stable geometries of the N and H atoms on the high symmetry adsorption sites of Ru@Cu54 NC have been studied. Although the N atom favours top and hollow sites, the H atom prefers to stay in the Ru-Cu bridge site along with the hollow sites. The adsorption energy of N on the Ru@Cu54 NC fcc site is found to be -5.42 eV, which is very close to the optimal value (-5.81 eV) of the ammonia decomposition volcano curve. The reaction energies for stepwise H atom elimination from an adsorbed NH3 molecule have been estimated. Finally, NH3 adsorption and decomposition on Ru@Cu54 have been illustrated in terms of electronic structure analysis. The energetics calculations for the dehydrogenation of NH3 suggest that Ru@Cu54 NC can be a suitable catalyst.

Parameters calculation method of energetic model for symmetrical static hysteresis loop and asymmetrical minor loop

PurposeThis paper aims to propose an energetic model parameter calculation method for predicting the materials’ symmetrical static hysteresis loop and asymmetrical minor loop to improve the accuracy of electromagnetic analysis of equipment.Design/methodology/approachFor predicting the symmetrical static hysteresis loop, this paper deduces the functional relationship between magnetic flux density and energetic model parameters based on the materials’ magnetization mechanism. It realizes the efficient and accurate symmetrical static hysteresis loop prediction under different magnetizations. For predicting the asymmetrical minor loop, a new algorithm is proposed that updates the energetic model parameters of the asymmetrical minor loop to consider the return-point memory effect.FindingsThe comparison of simulation and experimental results verifies that the proposed parameters calculation method has high accuracy and strong universality.Originality/valueThe proposed parameter calculation method improves the existing parameter calculation method’s problem of relying on too much experimental data and inaccuracy. Consequently, the presented work facilitates the application of the finite element electromagnetic field analysis method coupling the hysteresis model.

Cryo-EM structures of the D290V mutant of the hnRNPA2 low-complexity domain suggests how D290V affects phase separation and aggregation

hnRNPA2 is a human ribonucleoprotein that transports RNA to designated locations for translation via its ability to phase separate. Its mutated form, D290V, is implicated in MultiSystem Proteinopathy known to afflict two families, mainly with myopathy and Paget’s Disease of Bone. Here, we investigate this mutant form of hnRNPA2 by determining cryo-EM structures of the recombinant D290V low complexity domain (LCD). We find that the mutant form of hnRNPA2 differs from the wildtype fibrils in four ways. In contrast to the wildtype fibrils, the PY-nuclear localization signals in the fibril cores of all three mutant polymorphs are less accessible to chaperones. Also, the mutant fibrils are more stable than wildtype fibrils as judged by phase separation, thermal stability, and energetic calculations. Similar to other pathogenic amyloids, the mutant fibrils are polymorphic. Thus, these structures offer evidence to explain how a D-to-V missense mutation diverts the assembly of reversible, functional amyloid-like fibrils into the assembly of pathogenic amyloid, and may shed light on analogous conversions occurring in other ribonucleoproteins that lead to neurological diseases such as ALS and FTD.

Two three‐electron bonds in two triatomic molecules? The cases of C2O and N2C in their ground states

AbstractThe chemical bonding of CO and NC is analyzed in this work through the topological quantum approach using the electronic localization function (ELF) at the CASSCF level and by energetic calculations at the CCSD(T) level using four different basis sets. The results show that the dissociation of the molecules occurs via cleavage of the C‐C bond in the case of CO, while in the case of NC, it occurs via cleavage of the N‐C bond. Furthermore, the results obtained with ELF show monosynaptic basins containing excess electrons and disynaptic basins with a low electron population. This leads us to indicate the existence of three‐center‐two‐electron bonds according to previous results. From the valence bond model, a series of resonance structures have been proposed that support our calculations. In addition, the proposed structures have an ionic nature, indicating a charge shift character.

Dynamics simulation, energetics calculation and experimental analysis of the intermolecular interaction between human neonatal ABL SH3 domain and its N-substituted peptoid ligands

Non-receptor tyrosine kinase of neonatal ABL (nABL) is distributed in the nucleus and cytoplasm of proliferating cells in embryo and neonate, and has been implicated in the pathogenesis of neonatal leukemia and other hematological diseases. The kinase contains a regulatory Src homology 3 (SH3) domain that can specifically recognize proline-rich peptide segments on its partner protein surface. In this study, we systematically investigated the N-substitution effect on the binding of an empirically designed proline-rich peptide p9 to nABL SH3 domain by integrating dynamics simulations, energetics calculations and fluorescence affinity assays. The p9 is an almost all proline-composed decapeptide, with only a sole tyrosine at its residue 4, which has been found to bind nABL SH3 domain at a micromolar level in a class I mode. Here, the non-key residues of p9 peptide were independently replaced by various N-substituted amino acids to create a systematic N-substitution profile, from which we can identify those favorable, neutral and unfavorable substitutions at each peptide residue. On this basis a combinatorial peptoid library was rationally designed by systematically combining the favorable N-substituted amino acids at non-key residues of p9 peptide, thus resulting in a number of its peptoid counterparts. The binding affinity of top peptoid hits was observed to be comparable with or improved moderately relative to p9 peptide, with Kd ranging between 3.1 and 76 μM. Structural analysis revealed that the peptoids can be divided into exposed, polar and hydrophobic regions from N- to C-termini, in which the polar and hydrophobic regions confer specificity and stability to the domain–peptoid interaction, respectively. In addition, a designed peptoid was also observed to exhibit 5.3-fold SH3-selectivity for nABL over cSRC, suggesting that the N-substitution can be used to improve not only binding affinity but also recognition specificity of SH3 binders. Communicated by Ramaswamy H. Sarma

Environment-dependent phase stabilities of titanium hydrides: First-principles prediction

Various phases of TiHx (x=1−2) were constructed, with all possible H-atom configurations being considered. The first-principles energetics calculations were performed to evaluate their formation preference and mechanical and thermodynamic stabilities. All the results were then combined to construct the stable and metastable phase stability diagrams of TiHx. It is suggested that many stable and metastable TiHx phases have very comparable formation energies and thus are likely to co-exist. Their relative stabilities are strongly depended on temperature (T) and the partial pressure of hydrogen (p(H2)). Over the entire T and p(H2) range of interest, γ-TiH and γ-TiH2 are the only two stable phases. ɛ-TiH, γ-TiH1.5, ɛ- and δ-TiH1.75, and ɛ-TiH2 can possibly present as metastable phases. These metastable phases are all mechanically stable, and have a thermodynamic tendency to continuously absorb or release H until reaching the equilibrium phases of γ-TiH2 or γ-TiH.

Harnessing the druggability at orthosteric and allosteric sites of PD-1 for small molecule discovery by an integrated in silico pipeline

The PD-1/PD-L1 interaction is a promising target for small molecule inhibitors in cancer immunotherapy, but targeting this interface has been challenging. While efforts have been made to identify compounds that target the orthosteric sites, no reports have explored the potential of small molecules to target the allosteric region of PD-1. Therefore, our study aims to establish a pipeline to identify small molecules that can effectively bind to either the orthosteric or allosteric pockets of PD-1. We categorized the PD-1 interface into two hot-spot zones (P-and N-zones) based on extensive analysis of its structural, dynamical, and energetic properties. These zones correspond to the orthosteric and allosteric PPI sites, respectively, targeted by monoclonal antibodies. We used a guided virtual screening workflow to identify hits from ∼7 million compounds library, which were then clustered based on structural similarity and assessed by interaction fingerprinting. The selective and diverse chemical representatives were subjected to MD simulations and binding energetics calculations to filter out false positives and identify actual binders. Binding poses metadynamics calculations confirmed the stability of the final hits in the pocket. This study emphasizes the need for an integrated pipeline that uses molecular dynamics simulations and binding energetics to identify potential binders for the dynamic PD-1/PD-L1 interface, due to the lack of small molecule co-crystals. Only a few potential binders were discovered from a large pool of molecules targeting both the allosteric and orthosteric zones. Our results suggest that the allosteric site has more potential than the orthosteric site for inhibitor design. The identified “computational hits” hold potential as starting points for in vitro evaluations followed by hit-to-lead optimization. Overall, this study represents an effort to establish a computational pipeline for exploring and enriching both the allosteric and orthosteric sites of PPI interfaces, “a tough but indispensable nut to crack”.

The role of various permutations of TiO2 and MoS2 nanolayers on the radiation tolerance of Cu-TMD and Cu-TMO nanocomposites

Cu-based nanocomposites (NCs) are expected to have high radiation tolerance. Here we focus on using titanium dioxide (TiO2) and molybdenum disulphide (MoS2) to investigate interactions of interface of Cu- transition metal dilucogenides (TMD) and Cu- transition metal oxide (TMO) NCs which have been called Cu-2D material NCs. We generate six configurations of NCs including Cu/ TiO2/Cu (Sample1), Cu/TiO2@Cu@TiO2/Cu (Sample2), Cu/TiO2@Cu@MoS2/Cu (Sample3), Cu/MoS2@Cu@TiO2/Cu (Sample4), Cu/MoS2@Cu@MoS2/Cu (Sample5), and Cu/ MoS2TiO2/Cu (Sample6) to suggest the best model for improving the radiation tolerance of Cu-2D material NCs. The irradiation tolerance simulations have been carried out under a collision cascade induced by 6 keV primary knock-on atom (PKA) by atomistic simulations. Results imply the radiation tolerance of the Sample4 and Sample5 NCs is higher than that of other studied NCs. In order to clarify the sink action of the interface of these two NCs, we evaluated radiation defects and thermodynamics properties of this region at 3, 6, and 9 keV PKA energy. The dissipated potential energy in Cu layers of the Sample4 interface is significantly higher than that of Sample5 interface for 6 and 9 keV of PKA energy. The results of energetic calculations indicate the defect formation energy is reduced in the vicinity of interfaces. Compared with the Sample4, the Sample5 has low segregation energy for the interstitial emission mechanism to annihilate vacancies. Also, the interface of Sample5 has a higher strength of interaction and attraction with vacancies due to the low value of vacancy formation energy (Evac).

Density functional theory study of NO adsorption on the transition metal M (M=Cu, Fe and Mn) modified TiO2 surface

To study the effect of different kinds of transition metals and their proportions on NO adsorption on TiO2 surface, the density functional theory (DFT) method was used to calculate the energetic, geometric structure and electronic structure of the adsorption of NO on transition metal M (M = Cu, Fe and Mn)-anatase TiO2 (101) surface. The above transition metals were adsorbed on anatase TiO2 (101) surface in three different adsorption ratios, which are single transition metal adsorption model, mixed 2:2 and 1:3 ratio models. On the basis of the study, 13 models were established to study the effects of transition metals and adsorption ratio on NO oxidation to determine the optimal adsorption model. It has been found from the energetic calculations that mixed adsorption model is more stable for the adsorption of NO. The results of electronic structure and charge distribution analysis showed that a large quantity of active electron clusters are distributed around Mn and Fe atoms, which are attached to a large area of N atoms in NO, indicating that Mn and Fe can provide more electrons for catalytic reaction and facilitate electron exchange between catalyst and NO. Among all the adsorption models, the 3Fe+1Mn–TiO2 and 3Mn+1Fe–TiO2 models are superior, i.e., they can exchange more electrons with NO before the catalytic reaction, which is conducive to the subsequent catalytic reaction.

Progress on lanthanide sesquioxide phase transition

The present work aims to bring an original approach to the understanding of the polymorphic transition of RE2O3 from the low-temperature polymorph to the higher-temperature polymorph: from the cubic C to the hexagonal A form or from the monoclinic C to the monoclinic B form, for which the transition temperatures depend intimately on the rare earth element. The view proposed here, focusing on the lanthanide sesquioxide series, from Nd2O3 to Dy2O3, includes crystallographic and energetic considerations, using both bulk and surface energy calculations. After a complete description of the polymorphic filiations based on A, B and C unit cells described on simplified RE cation stacking schemes, it will be shown that the growth of the crystallite size as a function of temperature explains the existence of such transitions for these sesquioxides.

Understanding the Aggregation of Model Island and Archipelago Asphaltene Molecules near Kaolinite Surfaces using Molecular Dynamics.

The solubility of asphaltenes in hydrocarbons changes with pressure, composition, and temperature, leading to precipitation and deposition, thereby causing one of the crucial problems that negatively affects oil production, transportation, and processing. Because, in some circumstances, it might be advantageous to promote asphaltene agglomeration into small colloidal particles, molecular dynamics simulations were conducted here to understand the impacts of a chemical additive inspired by cyclohexane on the mechanism of aggregation of model island and archipelago asphaltene molecules in toluene. We compared the results in the presence and absence of a kaolinite surface at 300 and 400 K. Cluster size analyses, radial distribution functions, angles between asphaltenes, radius of gyration, and entropic and energetic calculations were used to provide insights on the behavior of these systems. The results show that the hypothetical additive inspired by cyclohexane promoted the aggregation of both asphaltenes. Structural differences were observed among the aggregates obtained in our simulations. These differences are attributed to the number of aromatic cores and side chains on the asphaltene molecules as well as to that of heteroatoms. For the island structure, aggregation in the bulk phase was less pronounced than that in the proximity of the kaolinite surface, whereas the opposite was observed for the archipelago structure. In both cases, the additive promoted stacking of asphaltenes, yielding more compact aggregates. The results provided insights into the complex nature of asphaltene aggregation, although computational approaches that can access longer time and larger size scales should be chosen for quantifying emergent meso- and macroscale properties of systems containing asphaltenes in larger numbers than those that can currently be sampled via atomistic simulations.