Computational and Theoretical Chemistry最新文献

{"title":"Theoretical investigation on the reaction kinetics of H with furfural","authors":"Qiongxuan Zhu ,&nbsp;Lili Xing ,&nbsp;Liuchao Lian ,&nbsp;Jing Zhu ,&nbsp;Xuetao Wang","doi":"10.1016/j.comptc.2025.115190","DOIUrl":"10.1016/j.comptc.2025.115190","url":null,"abstract":"<div><div>The reaction between furfural and H plays a crucial role in its thermal decomposition, but its specific kinetic data are not yet available. We used a high-level quantum chemistry method to model the potential energy surface of the furfural + H system. According to the potential energy surface, H-addition to the C_ε site has the highest energy barrier, while H-addition to the C_δ position has the lowest energy barrier. In the low-temperature range of 298-600 K, H-abstraction is faster than preliminary H-addition reaction. However, the H-addition reaction dominates when T&gt;600K. Subsequent reaction pathways of the formed intermediates were also analyzed. The temperature and pressure dependence of rate constants were studied and discussed. This study reveals distinct behaviors in the rate constants for intermediates and bimolecular products across different temperature ranges. These findings could aid in developing more accurate kinetic models.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115190"},"PeriodicalIF":3.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143715742","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Isomorphic graphene-like building unit","authors":"Fernando Alvarez-Ramírez ,&nbsp;Ariel A. Valladares","doi":"10.1016/j.comptc.2025.115195","DOIUrl":"10.1016/j.comptc.2025.115195","url":null,"abstract":"<div><div>A novel structural unit is proposed for constructing crystalline materials and molecular systems by mimicking the morphologies of carbon in its sp² allotropic forms. The new family of layered graphene-like crystals in 2D lattices exhibit crown ether-like cycles. The proposed structures are not limited to a single chemical element, carbon, and have the potential to modulate electronic properties based on their composition. Nine combinations of atomic elements of the structural unit are presented, which give rise to structures whose electronic gaps can vary from zero to 2.597 eV for a B-N-S-Si combination of the basic unit. Depending on the atomic composition, this structural unit may give rise to unstable or stable structures. The elastic constant analysis shows that three of the proposed structures are mechanically stable, while only the N-C-O-Ni configuration is both mechanically and dynamically stable, which is confirmed by the absence of negative frequencies in the dispersion calculations.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115195"},"PeriodicalIF":3.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682226","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"What drives enhanced chloride recognition of squaramide-based receptors over urea and thiourea? A computational exploration in the gas-phase and various solvents","authors":"Yasin Gholiee","doi":"10.1016/j.comptc.2025.115191","DOIUrl":"10.1016/j.comptc.2025.115191","url":null,"abstract":"<div><div>Significant progress in anion recognition has been achieved through the development of synthetic receptors. Urea-, thiourea-, and squaramide-based molecules, known for hydrogen-bonding capabilities, have gained prominence in supramolecular chemistry. The superior anion recognition of squaramide-based receptors, compared to urea- and thiourea-based ones, is repeatedly attributed to the crucial involvement of C<img>H fragments. This study computationally investigates chloride recognition by nine symmetric urea-, thiourea-, and squaramide-based receptors, focusing on solvent effects, interactions, and intrinsic affinity. The findings suggest that while C<img>H fragments aid anion recognition in squaramide-based receptors, the absence of steric repulsion and the presence of attractive forces between amide NH groups in squaramide, unlike in urea and thiourea receptors, significantly enhances anion-binding ability. Although solvation energy becomes less favorable from urea to squaramide, negative gas-phase Gibbs free energy drives complex formation. The accuracy of computational results is validated by excellent correlation between experimental and calculated formation constants.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115191"},"PeriodicalIF":3.0,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682225","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Examining the power of BiXO3 (X = Cr, Cu) oxide-perovskites: A first-principles study for next-generation solar cells","authors":"Hadia Khalil ,&nbsp;Misbah Tabassum ,&nbsp;Jalil Ur Rehman ,&nbsp;Syed Mansoor Ali ,&nbsp;Rajeh Alotaibi","doi":"10.1016/j.comptc.2025.115194","DOIUrl":"10.1016/j.comptc.2025.115194","url":null,"abstract":"<div><div>The current study investigates the structural, electronic, optical, and mechanical aspects of Bi-based oxide-perovskites BiXO₃ (X = Cr, Cu) while using first-principles simulations. BiCrO₃ and BiCuO₃ have lattice parameters of 3.85 and 3.87 Å, respectively. Both the materials have semiconducting properties with a direct band gap as indicated by the band structure and density of states. The computed energy band gap for BiCrO₃ and BiCuO₃ is found 1.68 and 1.36 eV, respectively. To describe how light interacts with the material, the optical characteristics of both materials are examined for photon energies between 0 and 12 eV. Based on their mechanical properties, it is found that both materials are mechanically stable, hard, and incompressible. According to Cauchy pressure and Pugh's ratio, both the compounds show a ductile behavior. The overall investigation shows that both materials are appropriate for next generation solar cells.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115194"},"PeriodicalIF":3.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682227","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Substitution and coordination effects of boron in FeC and FeNC single-atom catalysts for ORR: A DFT study","authors":"L.L. Sun ,&nbsp;Z.Y. Wang ,&nbsp;Y.H. Wang ,&nbsp;Y. Wang ,&nbsp;Y.C. Li","doi":"10.1016/j.comptc.2025.115192","DOIUrl":"10.1016/j.comptc.2025.115192","url":null,"abstract":"<div><div>The development of durable and cost-effective cathode catalysts is critical to improving the oxygen reduction reaction (ORR) of fuel cells. The B-substituted Fe-based graphene single atom catalysts (SACs) were systematically analyzed using density functional theory (DFT). After analysis of the computational formation energy, 12 stable configurations are identified from 49 candidates. B-substituted in the first coordination sphere layer resulted in excessively strong adsorption of oxygen-containing intermediates, thereby increasing the overpotential. In contrast, the FeN₄B_<del>4</del> and FeN₄B₅ catalysts, with B substitution in the second coordination sphere, exhibited low overpotentials of 0.32 V and 0.36 V, respectively. This enhancement is attributed to the B-atom-induced reconfiguration of the electronic structure and modulation of chemical bonding properties.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115192"},"PeriodicalIF":3.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Two bond-exchange modes in sodium silicate liquids: Slide and oscillation modes","authors":"Fumiya Noritake","doi":"10.1016/j.comptc.2025.115196","DOIUrl":"10.1016/j.comptc.2025.115196","url":null,"abstract":"<div><div>The network structure of polymerized silicate liquids suppresses the diffusion mechanism of silicon and oxygen atoms. Several diffusion model for these network forming elements have been presented based on nuclear magnetic resonance spectroscopy and molecular dynamics simulations. The authors' previous study introduced the concept of bond-breaking/forming particle, that can analyze quantitatively the certain bond exchange event from pair correlation functions of those particles. In this study, the angular part of the pair-correlation function of bond-breaking/forming particles was introduced, and an atomistic description of the two different bond exchange modes, that found in the author's previous study, was revealed. The first peak represent exchange of Si<img>O bonds in a sliding manner, whereas the second peak correspond to exchange in an oscillating manner. The inner product of vectors correspond to broken and newly formed bond is zero to positive in former mode, negative in latter mode.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115196"},"PeriodicalIF":3.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682223","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Uniaxial strain effects on the electronic and thermoelectric properties of SnSe monolayer: A density functional theory study","authors":"Erik Bhekti Yutomo ,&nbsp;Fatimah Arofiati Noor ,&nbsp;Toto Winata","doi":"10.1016/j.comptc.2025.115184","DOIUrl":"10.1016/j.comptc.2025.115184","url":null,"abstract":"<div><div>The effect of uniaxial strain on the structural, electronic, and thermoelectric properties of SnSe monolayer was investigated using density functional theory combined with Boltzman transport theory. We consider two different uniaxial strain directions: zigzag, and armchair directions. Highly anisotropic linear Poisson ratios were observed under uniaxial strains. A nonlinear relationship between bandgap with uniaxial strain manifests under zigzag-directed uniaxial strain. Then, bandgap decreases as uniaxial strain along armchair direction is increased. The Seebeck coefficient increased to 1.60 mV/K under a 2 % zigzag-directed uniaxial strain; this increase is closely associated with band convergence conditions in this system. Furthermore, 1 % of uniaxial strain along zigzag and armchair directions has optimized the ideal thermoelectric figure of merit at 300 K. This is due to the combination of moderate Seebeck coefficient and low electronic thermal conductivity. Our results provide a route for optimizing the thermoelectric properties of SnSe monolayer by strain engineering.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115184"},"PeriodicalIF":3.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682220","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling the potential of C4N3 as a novel sensing surface for persistent organic pollutants: A DFT study","authors":"Mehvish Perveen ,&nbsp;Muhammad Zahid ,&nbsp;Javed Iqbal ,&nbsp;Hafeez Anwar","doi":"10.1016/j.comptc.2025.115193","DOIUrl":"10.1016/j.comptc.2025.115193","url":null,"abstract":"<div><div>Persistent organic pollutants (POPs) pose severe environmental and public health risks due to their accumulation in biological systems. This study investigates the feasibility of carbon nitride (C₄N₃) as a sensing material for the detection of POPs using DFT studies. The adsorption characteristics of three model POPs dibenzofuran (DB), benzopyrene (BP), and benzodioxine (BX) were calculated. The adsorption-energies (Ead) illustrate Van-der Waals interactions, further evidenced by the non-covalent interaction analysis and quantum-theory of atoms in molecules analysis. The electronic properties of the systems (DB@C₄N₃, BP@C₄N₃, and BX@C₄N₃) were evaluated using the molecular electrostatic potential, natural bond orbital analysis, density of state calculations, and electron-localization function. NBO analysis indicated charge transfer from the C₄N₃ surface to the analytes. The recovery time was determined using transition-state theory to assess the reusability. These results offer a theoretical basis for potentially utilizing the C₄N₃ surface in sensors that target major POPS in the environment.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115193"},"PeriodicalIF":3.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Calcite nano-structure as a novel drug carrier for 5-Fluorouracil chemotherapy agent: A computational study using DFT and AIMD","authors":"Lazya Aziz Mirza ,&nbsp;Rangeen Othman Salih ,&nbsp;Nzar Rauf Abdullah","doi":"10.1016/j.comptc.2025.115181","DOIUrl":"10.1016/j.comptc.2025.115181","url":null,"abstract":"<div><div>Calcium carbonate (<span><math><msub><mrow><mi>CaCO</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span>) is regarded as a promising next-generation drug delivery technology owing to its biocompatibility, pH-sensitive properties, nontoxicity, and cost-effectiveness. Calcite, one of the thermodynamically stable anhydrous polymorphic forms of <span><math><msub><mrow><mi>CaCO</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span>, has been utilized in drug delivery systems in various laboratory-based studies. However, no ab initio studies have been conducted on the use of three-dimensional nanostructures of calcite as drug carriers. This work examines a unit cell of calcite as a novel drug delivery system for the chemotherapy drug 5-Fluorouracil (5-FU), utilizing density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The results indicate a significant interaction between calcite and 5-FU, with no alterations observed in the molecular geometry. The interaction occurred as a result of charge transfer from the calcite to the molecule. The density of states and absorption spectra of calcite and the 5-FU+calcite complex are studied. The results indicate that calcite exhibits semiconductor characteristics, whereas the complex displays metallic characteristics. In addition, the stability of the complex at human body temperature is investigated using AIMD simulations. The findings indicate that the interaction persists at 310 K and elevated temperatures, with no significant increase in the distance between 5-FU and calcite. The dissolution of calcite in the presence of hydrogen ions (<span><math><msup><mrow><mi>H</mi></mrow><mrow><mo>+</mo></mrow></msup></math></span>) ions, indicative of the acidic environment surrounding tumors, facilitates the release of the 5-FU molecule without alterations to its geometry. Ultimately, the results indicate that calcite effectively bonds with 5-FU, maintaining interaction at human body temperature and facilitating release through dissolution in proximity to tumors.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115181"},"PeriodicalIF":3.0,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Role of homonuclear B–B/N–N bonds in DNA nucleobases adsorption on boron nitride fullerenes: Biosensor and drug transport implications","authors":"Gabriel García-Laiton ,&nbsp;Fernando Arcenio Zubieta López ,&nbsp;Ehsan Shakerzadeh ,&nbsp;Ernesto Chigo-Anota","doi":"10.1016/j.comptc.2025.115188","DOIUrl":"10.1016/j.comptc.2025.115188","url":null,"abstract":"<div><div>The potential of boron nitride fullerenes (BNFs) as sensors or drug delivery platforms was investigated through the adsorption of DNA nucleobases (adenine, guanine, cytosine, and thymine) on B₁₂N₁₂-36HT (insulating) and B₁₂N₁₂-9HM (semiconducting) structures. Density Functional Theory (DFT) calculations with the HSEh1PBE functional and 6-311G(d,p) basis set were performed to analyze adsorption mechanisms, reactivity, and electronic properties in gas and aqueous phases. Cytosine and thymine formed covalent C=O–B bonds, while adenine and guanine exhibited NH–B interactions. Anionic states were dominated by dispersive NH–N and CH–N interactions, whereas cationic complexes displayed B–O/B–N bonding in gas and van der Waals forces in water. Quantum descriptors, such as adsorption energy, |HOMO-LUMO| gap, chemical potential, and work function, revealed that homonuclear B<img>B and N<img>N bonds significantly enhance adsorption strength, solubility, and conductivity. These findings underscore the potential of BNFs as platforms for biosensors and drug delivery.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115188"},"PeriodicalIF":3.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143636837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}