Journal of Molecular Modeling最新文献

{"title":"In depth first-principles investigation of phase stability, structural, vibrational, electronic, elastic, piezoelectric, and magnetic properties in vanadium-based janus dichalcogenide monolayer VBrSe","authors":"Laichaoui Mahdi Mourad,&nbsp;Rami Mrad,&nbsp;Yuanping Chen,&nbsp;Shibing Chu","doi":"10.1007/s00894-025-06444-2","DOIUrl":"10.1007/s00894-025-06444-2","url":null,"abstract":"<div><h3>Context</h3><p>This study presents a comprehensive first-principles investigation of the structural, electronic, vibrational, elastic, and piezoelectric properties of monolayer Janus VBrSe in both 2<i>H</i> and 1<i> T</i> phases. The 1<i> T</i> phase is found to be dynamically unstable, whereas the 2<i>H</i>-VBrSe phase is confirmed to be both energetically favorable and dynamically stable, indicating its feasibility for experimental synthesis. The 2<i>H</i> phase exhibits a direct band gap with pronounced strain sensitivity, significant out-of-plane piezoelectric response, and distinct Raman-active vibrational modes, facilitating phase identification. Micromagnetic simulations further reveal robust ferromagnetic ordering. These properties establish 2<i>H</i>-VBrSe as a multifunctional material suitable for next-generation applications in sensors, optoelectronics, flexible devices, and spintronic systems.</p><h3>Methods</h3><p>Density functional theory (DFT) calculations were performed using the VASP package, incorporating spin–orbit coupling and van der Waals corrections to accurately capture the behavior of layered systems. Electronic structure and geometry were optimized using advanced exchange–correlation functionals to improve band gap accuracy. Phonon dispersion analyses confirmed dynamic stability, while elastic constants and piezoelectric coefficients were computed to assess mechanical and electromechanical performance. Ferromagnetic behavior was evaluated via micromagnetic simulations using MuMax3. The theoretical framework enables further exploration of temperature-dependent phenomena, such as thermal stability and dynamical response, through ab initio molecular dynamics.</p></div>","PeriodicalId":651,"journal":{"name":"Journal of Molecular Modeling","volume":"31 8","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144717236","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Noncovalent dyads of lanthanide nitride cluster fullerenes Ln3N@C80 and bisphthalocyanines LnPc2: Insights from DFT calculations","authors":"Lina M. Bolivar-Pineda,&nbsp;Elena V. Basiuk,&nbsp;Vladimir A. Basiuk","doi":"10.1007/s00894-025-06415-7","DOIUrl":"10.1007/s00894-025-06415-7","url":null,"abstract":"<div><h3>Context</h3><p>Lanthanide-based systems, such as nitride cluster fullerenes Ln₃N@C₈₀ and bipthalocyanines LnPc₂ (Pc = phthalocyanine ligand), are of interest for their magnetic, fluorescent and electronic properties. In this regard, we performed DFT characterization to investigate the changes in structure and electronic properties for noncovalently interacting lanthanide (Ln; where Ln = La, Ce, Gd and Lu) nitride cluster fullerenes and bisphthalocyanines to form Ln₃N@C₈₀ + LnPc₂ dyads. The optimized geometries, formation and frontier orbital energies, HOMO-LUMO plots, charge and spin of Ln and N(NCF) atoms, as well as spin density plots of the dyads were analyzed in comparison with those of isolated Ln₃N@C₈₀ and LnPc₂ components. In addition to LnPc₂ bending distortion, the noncovalent dyad formation alters the geometry of the encapsulated Ln₃N cluster, favoring more planar or pyramidal geometries, depending on the case. The HOMO and LUMO orbitals are found on bisphthalocyanines, being localized on the isoindole units, except for Ce₃N@C₈₀ + CePc₂ dyad, where the LUMO was found on the central metal of CePc₂. The HOMO-LUMO gap energy is lower for the dyads compared to isolated NCFs, being rather close to the gap energy of bisphthalocyanines. The changes in spin density distribution are evident in the dyads containing Ce and Gd atoms, contrary to their La and Lu-derived counterparts. The interaction of Ce₃N@C₈₀ and Gd₃N@C₈₀ with CePc₂ and GdPc₂, respectively, causes redistribution of the spin density, with changes in the orientation of spin-up and spin-down electrons in the encapsulated Ce₃N and Gd₃N clusters.</p><h3>Methods</h3><p>The geometry optimization and electronic properties calculations based on density functional theory were performed using the DMol³ module of Material Studio 8.0 software package from Accelrys Inc. The computational parameters selected included the general gradient approximation functional PBE, combined with a long-range dispersion correction developed by Grimme (PBE-D2), the double numerical basis set (DN), equivalent to the 6-31G Pople-type basis set along with the DFT semiconductor pseudopotentials. To mitigate the self-consistent field convergence problems, the thermal smearing technique was applied, with a final very small value of 0.0001 Ha (equivalent to 31.6 K temperature), or Fermi orbital occupancy in some cases.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":651,"journal":{"name":"Journal of Molecular Modeling","volume":"31 8","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12287152/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144697338","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multi-fidelity neural network–based prediction of tensile strength of high-entropy alloy (FeNiCoCrCu) using molecular dynamics data","authors":"Nazib E Elahi Khan Chowdhury,&nbsp;Alif Jawad,&nbsp;Anfalur Rahman,&nbsp;Mohammad Jane Alam Khan","doi":"10.1007/s00894-025-06439-z","DOIUrl":"10.1007/s00894-025-06439-z","url":null,"abstract":"<div><h3>Context</h3><p>High-entropy alloys (HEAs) represent a class of advanced materials with superior mechanical, thermal, and chemical properties. FeNiCoCrCu HEA has been of particular interest due to its excellent tensile strength, corrosion resistance, and thermal stability. However, it is a significant challenge to understand and optimize the mechanical properties of such alloys due to the complex structure. Molecular dynamics (MD) is a popular choice in investigating atomic-scale characteristics but is computationally costly for large polycrystal systems. Machine learning approaches have seen growing interest as surrogate models that can produce accurate predictions and lower computational costs. This study demonstrates the first application of Multi-fidelity Physics Informed Neural Network (MPINN) model for predicting the tensile strength of FeNiCoCrCu. This study generates a large dataset of tensile strength for different compositions of FeNiCoCrCu HEA and uses it to train a MPINN model. The MPINN model successfully predicts the tensile strength of FeNiCoCrCu for different compositions and validates the effectiveness of the MD data-enabled MPINN model in making accurate predictions of material properties.</p><h3>Methods</h3><p>This study uses LAMMPS for the molecular dynamics simulations and TensorFlow for building and running the machine learning models. The low-fidelity (LF) and high-fidelity (HF) data for the machine learning model are obtained from MD simulations of small single crystals and large polycrystals, respectively. MD simulation systems are created using Atomsk, and EAM potential is used for the forcefield. The simulations are visualized using OVITO. The MPINN model utilizes both linear and non-linear relations between LF and HF data. In TensorFlow, the machine learning model is optimized using the Adam optimizer, and L2 regularization is used to prevent overfitting.</p></div>","PeriodicalId":651,"journal":{"name":"Journal of Molecular Modeling","volume":"31 8","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144688540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"New determination of the thermophysical properties of argon gas considering nuclear spin and symmetry effects","authors":"F. Bouchelaghem,&nbsp;H. Boutarfa,&nbsp;M. Chicouche,&nbsp;S. Lias","doi":"10.1007/s00894-025-06435-3","DOIUrl":"10.1007/s00894-025-06435-3","url":null,"abstract":"<div><h3>Context</h3><p>Since statistical physics and quantum mechanics were first successfully combined thanks in part to the work of Chapman and Cowling and Hirschfelder. Extensive theoretical and experimental research has been dedicated to understanding the kinetics of gases and gas mixtures. This integration has, among other achievements, theoretically established a direct link between the macroscopic properties of gases whether measured or calculated and the quantum characteristics of their constituent particles. This model successfully established straightforward mathematical relationships linking the microscopic interactions between the atomic and/or molecular components of a gas to measurable transport properties, such as diffusion and viscosity coefficients. It also provided explanations for how these properties vary and how they are influenced by thermodynamic parameters like pressure, density, and temperature.</p><h3>Methods</h3><p>The potential data available to us are either obtained from ab initio calculations or experimental measurements. The ab initio values of the potential <i>V</i>(<i>R</i>) are derived from a quantum-theoretical approach to the molecular problem. Typically, these methods provide the potential energy at discrete values of the internuclear distance <i>R</i> within a specified range. To build the potential energy curve corresponding to the fundamental interactions, we will rely on ab initio data. Knowing this potential allows for the numerical solution of the radial wave equation using Numerov’s method, ultimately enabling the calculation of the phase shifts <span>(eta left( Eright) )</span>. From the elastic collision phase shifts, we derive the self-diffusion coefficient <i>D</i>, viscosity <span>(eta )</span>, and thermal conductivity <span>(lambda )</span> using the Chapman-Enskog model. For diffusion and viscosity, we perform calculations both with accounting for the symmetry and spin effects associated with the identical nature of the colliding particles. We then examine how these transport coefficients vary with temperature and propose a straightforward computational approach to obtain analytical expressions for <i>D</i>(<i>T</i>), <span>(eta (T))</span>, and <span>(lambda (T).)</span></p></div>","PeriodicalId":651,"journal":{"name":"Journal of Molecular Modeling","volume":"31 8","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144688541","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Density functional theory for nanomaterials: structural and spectroscopic applications—a review","authors":"Ansa Latif,&nbsp;Anam Latif,&nbsp;Muhammad Mohsin,&nbsp;Ijaz Ahmad Bhatti","doi":"10.1007/s00894-025-06431-7","DOIUrl":"10.1007/s00894-025-06431-7","url":null,"abstract":"<div><h3>Context</h3><p>Nanoparticles (NPs) exhibit unique physical and chemical properties that defy classical mechanics, owing to their quantum nature. These properties are dictated by size, shape, and structure, rendering NPs indispensable across diverse applications, including catalysis, medical imaging, drug delivery, and energy research. Advanced computational tools have become indispensable in unraveling the intricacies of nanomaterial behavior, driving significant progress in theoretical and computational research. Among these tools, the density functional theory (DFT) has emerged as a powerful method for predicting material properties. In this review study, we delve into key aspects of DFT simulations applied to nanomaterials, including Optimal Geometries, Band Gap and Electronic Properties, Density of States (DOS), Natural Bond Orbitals (NBO), and spectroscopic features (Infrared, Raman Spectra, and UV–Visible Spectra). Despite its successes, DFT faces limitations, particularly concerning semiconductor materials. Researchers strive to enhance its accuracy while maintaining computational efficiency. Balancing generically accurate functionals for specific applications remains an ongoing challenge. As nanomaterial continues to play a significant part in a variety of industries, the progress of DFT is of great interest and exploration.</p><h3>Methods</h3><p>This review discusses DFT-based computational techniques employed for modeling nanomaterials. The calculations are generally done by utilizing generalized gradient approximation (GGA) functionals such as PBE (Perdew–Burke–Ernzerhof), and where necessary, hybrid functionals like B3LYP to enhance band gap accuracy. All calculations are performed using the standard quantum chemistry packages such as VASP, Gaussian, or Quantum ESPRESSO. This combination of methods offers a complete theoretical basis for the study of nanomaterial properties.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":651,"journal":{"name":"Journal of Molecular Modeling","volume":"31 8","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144666807","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Microhydration of phenylboronic acid and its hydration free energy","authors":"Doungous Sale,&nbsp;Alhadji Malloum,&nbsp;Mama Nsangou,&nbsp;Jean Jules Fifen,&nbsp;Jeanet Conradie","doi":"10.1007/s00894-025-06436-2","DOIUrl":"10.1007/s00894-025-06436-2","url":null,"abstract":"<div><h3>\u0000 <b>Context</b>\u0000 </h3><p>Understanding the interactions of phenylboronic acid with its surrounding water molecules is essential for several applications in solvated systems. In the present work, we investigated the microhydration of the phenylboronic acid (PBA) and calculated its hydration free energy using the cluster continuum solvation model. Microhydration of PBA has not been investigated previously in the literature. It requires the structures of PBA to be surrounded by <i>n</i> explicit water molecules (PBA-W<span>(_n)</span>). The results show that the B(OH)<span>(_2)</span> unit of phenylboronic acid forms clusters with water molecules that are similar to those of neutral water clusters. The QTAIM analysis shows that the structures of phenylboronic acid-water clusters are stabilized by strong OH<span>(cdots )</span>O and weak CH<span>(cdots )</span>O hydrogen bonds. In addition to QTAIM analysis, NBO analysis was also performed on the most stable configurations to better understand the delocalization of electron density from donor to proper acceptor within the compound. In addition, we found that the most stable structures dominate the population of the clusters for temperatures from 20 to 400 K. Finally, using the structures of the microhydrated phenylboronic acid, we estimated the free energy of hydration and the enthalpy of hydration of PBA. At room temperature, the phenylboronic acid’s free energy and enthalpy of hydration are respectively evaluated to be <span>(-)</span>72.1 kcal/mol and <span>(-)</span>85.5k cal/mol. Assessment of temperature effects on the free energy and the enthalpy of hydration shows that the enthalpy is temperature-independent, while the free energy increases linearly with temperature.</p><h3>\u0000 <b>Methods</b>\u0000 </h3><p>Initial configurations of PBA-W<span>(_n)</span> have been generated using classical molecular dynamics and subsequently optimized using the level of theory, <span>(omega )</span>B97X-D/def2-TZVP. Optimizations, frequency calculations, and NBO analysis are performed using the Gaussian 16 suite of programs. On the most stable configurations, we have performed the quantum theory of atoms in molecules (QTAIM) analysis to get insights into the hydrogen bond network of PBA-W<span>(_n)</span>. QTAIM is performed using AIMAll software. Thermodynamic properties as a function of temperature are evaluated using a homemade FORTRAN code-named <b>TEMPO</b>.</p></div>","PeriodicalId":651,"journal":{"name":"Journal of Molecular Modeling","volume":"31 8","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12276122/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144666808","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical modeling of interactions of Cr2On and Mn2On clusters with H2 molecules","authors":"Konstantin V. Bozhenko,&nbsp;Andrey N. Utenyshev,&nbsp;Lavrenty G. Gutsev,&nbsp;Sergey M. Aldoshin,&nbsp;Gennady L. Gutsev","doi":"10.1007/s00894-025-06437-1","DOIUrl":"10.1007/s00894-025-06437-1","url":null,"abstract":"<div><h3>Context</h3><p>Gas sensors with high sensitivity and selectivity are essential for industrial safety and environmental monitoring. The ongoing development of more effective sensors relies on two key aspects: the design of novel sensing materials and a deeper understanding of the underlying sensing mechanisms. Among the various materials used for the sensor fabrication, semiconducting metal oxides such as chromium and manganese oxides have garnered much recent attention. Notably, palladium-doped chromium oxide has demonstrated high efficiency in hydrogen sensing. Chromium oxides can function as single-component sensors and also in components of composite systems. Manganese oxides are likewise widely used in sensing applications, especially as electrochemical sensors either alone or in combination with other metal oxides.</p><h3>Methods</h3><p>All calculations were carried out by using spin-polarized density functional theory with the generalized gradient approximation as implemented in Gaussian 09. Among the numerous exchange–correlation functionals and basis sets, we chose the BPW91 functional and 6–311 + G* basis set of triple-zeta quality. We considered reactions of Cr₂O_<i>n</i> and Mn₂O_<i>n</i> with H₂ and found pathways leading from the reagents to products. All but one reaction pathways were found to have two or three transition states separated by local minima. The search of transition states was performed by using the modified conjugate gradient algorithm and the local minima were determined by applying the intrinsic reaction coordinate algorithm. It was found that some of the pathways are spin-dependent, i.e., the total spin magnetic moments of reagents do not match those of the products.</p></div>","PeriodicalId":651,"journal":{"name":"Journal of Molecular Modeling","volume":"31 8","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144666809","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Potential use of deep eutectic solvents based on sugar as green separation media for the acidic gases capture process from the gas mixtures: molecular dynamics simulation and COSMO-RS insights","authors":"Samaneh Barani Pour,&nbsp;Nasrin Jabbarvand Behrooz,&nbsp;Jaber Jahanbin Sardroodi,&nbsp;Mohammad Sadegh Avestan","doi":"10.1007/s00894-025-06430-8","DOIUrl":"10.1007/s00894-025-06430-8","url":null,"abstract":"<div><h3>Context</h3><p>The global greenhouse gas (GHG) emissions originate from five main economic sectors: energy, industry, construction, transportation, and AFOLU (agriculture, forestry, and other land uses). The emissions of these gases from fossil fuels and land use have reached their highest levels since the nineteenth century. Consequently, urgent actions are required to address this issue worldwide to deal with specific challenges affecting air quality and weather conditions. For this purpose, the reduction of environmental pollutants requires finding methods, including extraction techniques using green solvents (DESs). Understanding the interactions between acid gases (H₂S/CO₂) and the eutectic solvent components (HBA/HBD) determines how much pollutant is absorbed by deep eutectic solvents (DESs). In this regard, to better comprehend the mechanism of H₂S gas absorption, we calculated the combined distribution functions (CDFs) involving the radial distribution functions (RDFs) and the angular distribution functions (ADFs). Additionally, we examined the hydrogen-bonding network, density profiles, spatial distribution functions (SDFs), and the nonbonded energies between H₂S and DES (choline chloride (ChCl)-glucose (Glu)/fructose (Fru) with a molar ratio of 2:1) components were calculated at 333 K. Furthermore, at the pressure between 1 and 15 atm, we obtained the solubility of H₂S/CO₂ gases, solubility selectivity, and diffusivity selectivity parameters as pressure functions to assess the efficacy of sugar-based DES in natural gas sweetening procedures. By analyzing how the interaction of H₂S molecules with the DES components, we concluded that the eutectic solvents based on glucose (Glu)/fructose (Fru) and choline chloride (ChCl) can absorb H₂S molecules.</p><h3>Methods</h3><p>The molecular graphics program VMD and the PACKMOL package have been used to prepare DES components and simulation boxes. First, initial configurations were minimized under the periodic boundary condition, and then the systems were heated to T = 333 K. Then, a 50 ns NPT simulation was performed at 333 K, while gradually decreasing the distance between the two boxes until reaching equilibrium. The conductor-like screening model (COSMO), as a novel method, has been utilized to predict some properties. The TURBOMOLE program package has been employed to determine the geometries of the electronic density of each HBA and HBD in targeted deep eutectic solvents (optimizing the geometry of DESs components with Becke–Perdew-86 (BP86) functional along with a triple zeta valence potential (TZVP) basis set).</p></div>","PeriodicalId":651,"journal":{"name":"Journal of Molecular Modeling","volume":"31 8","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144625238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"How does the conformational landscape change on replacement in tetralin? A computational investigation with oxygen, sulfur, and selenium","authors":"Asif Iqubal Middya,&nbsp;Abhijit Chakraborty","doi":"10.1007/s00894-025-06432-6","DOIUrl":"10.1007/s00894-025-06432-6","url":null,"abstract":"<div><h3>Context</h3><p>The oxygen, sulfur, and selenium derivatives of tetralin termed as isochroman (IC), isothiochroman (ITC), and isoselenochroman (ISC) showed interesting conformational patterns. In particular, ITC and IC have immense pharmacological significance. The twisted conformer is the global minimum in IC, where the bent is a transition state (TS) and remains 1100 ± 100 cm⁻¹ higher. The bent form in ITC and ISC possesses the lowest energy. But, the twisted conformer lies higher by about 80 ± 20 cm⁻¹ in ITC and 700 ± 50 cm⁻¹ in ISC. The potential energy surfaces (PES) locate all the conformations and TSs. Molecular electrostatic potentials indicate the sites of electrophilic interactions, and the small energy difference between the minima in ITC predicts an interesting interplay of intermolecular interactions in suitable environments. The validity of the maximum hardness principle and minimum electrophilicity principles is checked. Frontier molecular orbitals show the change in electron densities on excitation, which are mostly π → π^* in nature. Hyperconjugative interactions involving different <i>σ</i> and lone pair orbitals explain the change in conformational patterns in these molecules. We suggest some experiments to corroborate our findings.</p><h3>Methods</h3><p>Computations are performed with different functionals (B3LYP, M06-2X, and ωB97X-D) in DFT as well as ab initio methods (MP2 and CCSD) with 6-311G +  + (2d, 3p) and augmented cc-pVDZ as basis sets. Gaussian 09 is used for the above computations. PED analyses were performed by Veda 4 software. For viewing and plotting purposes, Gaussview 5.0 and Origin 8.5 are used.</p></div>","PeriodicalId":651,"journal":{"name":"Journal of Molecular Modeling","volume":"31 8","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144615703","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Screening of ionic liquids as sustainable catalyst for production of n-butyl acetate using COSMO-RS model","authors":"Anantharaj Ramalingam,&nbsp;Achsah Rajendran Startha Christabel,&nbsp;Gayathri Mahavishnu","doi":"10.1007/s00894-025-06434-4","DOIUrl":"10.1007/s00894-025-06434-4","url":null,"abstract":"<div><h3>Context</h3><p>A total of 42 cations and 32 anions resulting in 1344 possible combinations were screened for green esterification process via the conductor-like screening model for real solvents (COSMO-RS model). The esterification reactants and products; n-butanol (n-BuOH), acetic acid (HAc), and n-butyl acetate (n-BuAc) in different combination of cation and anions were used to predict the activity coefficient at infinite dilution (IDAC) with the help of screening charge density. From the predicted IDAC values, the selectivity (S), capacity (C), and performance index (PI) were calculated to screen potential ionic liquids (ILs) for the green esterification process. Further, the σ-profile, and σ-potential of ILs, reactants, and products were generated and analysed.</p><h3>Methods</h3><p>Molden Visualization Software, Gaussian 03 software, COSMOthermX (Version:19.0.5) were used to predict IDAC, sigma profile, and sigma potential. Hartree–Fock level and basis set 6-31G*. Density functional theory (DFT) with PBVP86 in combination with the basis set SVP (split valence polarised) and the density fitting basis set DGA1 (density gradient approximation)—#P BVP86/SVP/DGA1.</p></div>","PeriodicalId":651,"journal":{"name":"Journal of Molecular Modeling","volume":"31 8","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144615705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}