Computational and Theoretical Chemistry最新文献

{"title":"A theoretical evaluation of the multiple radical scavenging reactions of Hibiscetin","authors":"C. Ragi,&nbsp;K. Muraleedharan","doi":"10.1016/j.comptc.2025.115207","DOIUrl":"10.1016/j.comptc.2025.115207","url":null,"abstract":"<div><div>Density functional theory has been used to study the multiple free radical scavenging properties of the most hydroxylated flavonol, Hibiscetin in the gas, benzene, and water phases. The antioxidant activity of the hydroxyl group is decreased by intramolecular hydrogen bonds, which act as hydrogen bond donors, and increases by hydrogen bond acceptors. The continuous di‑hydrogen atom transfer (HAT) reaction from the catechol groups creates stable quinones in the gas and benzene phases. The penta-HAT mechanism is preferred in the Gas phase and benzene medium, both generating di-quinone 3′-radical. There was no possibility of further HAT, as shown by the high BDE values (&gt;100 kcal/mol). The Frontier molecular orbital and molecular electrostatic potential analyses complement the findings. Hibiscetin prefers to undergo sequential proton loss reactions in the aqueous phase, yielding a hepta anion which then undergoes five successive electron transfer processes to generate the di-quinone di-anion-radical. The free energy calculation with specific reactive oxygen radicals validates the results. The discovery is further supported by the gas phase basicity (GPB) and pKa calculation. The initial pKa is 8.7 and GPB is 316.2, both of which are in agreement with findings from related compounds published in the literature.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115207"},"PeriodicalIF":3.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734518","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":"Exploring the adsorption properties of PTFE-decorated and metal doped covalent organic frameworks for environmental cleanup: A computational outlook","authors":"Bassey E. Inah ,&nbsp;N. Favour Azogor ,&nbsp;Hannah Tom Akpan ,&nbsp;Okereke E. Levi ,&nbsp;Destiny Charlie ,&nbsp;Adebayo P. Adeleye","doi":"10.1016/j.comptc.2025.115202","DOIUrl":"10.1016/j.comptc.2025.115202","url":null,"abstract":"<div><div>This study explores the adsorption behavior of poly-tetra-fluoro-ethylene (PTFE)-decorated and metal (Fe, Li)-doped covalent organic framework (COF) surfaces for environmental remediation, specifically targeting crude oil components (benzene, ethylbenzene, toluene, and xylene). Using Density Functional Theory (DFT) calculations, key electronic properties such as Frontier Molecular Orbital (FMO) parameters, Natural Bond Orbital (NBO) analysis, Density of States (DOS), adsorption energies, and charge transfer mechanisms were evaluated. Results indicate that PTFE decoration promotes moderate physisorption, with band gaps ranging from 0.1 eV to 5.5 eV. Notably, PTFE-COF exhibits a narrow energy gap of 0.146 eV, with minimal change upon interaction with benzene (0.147 eV). However, xylene and toluene interactions increase the energy gap to 0.432 eV and 0.883 eV, respectively. Metal doping significantly alters adsorption behavior; Fe doping enhances chemisorption, while Li doping has a mixed effect, increasing the band gap in some cases (e.g., Ethylbenzene_Li@PTFE-COF at 5.5 eV). Adsorption energies range from 0.00265 MeV to 0.00274 MeV, indicating interactions between weak chemisorption and moderate physisorption. Reduced density gradient (RDG) analysis reveals a combination of van der Waals and steric repulsive interactions, particularly around boron‑oxygen sites. Charge transfer analysis confirms efficient electron redistribution, while dipole moment and current density evaluations highlight Toluene_PTFE-COF as exhibiting the highest sensitivity (−3.49 × 10¹³ A/m²) among the studied systems. These findings offer valuable insights into the design of COF-based materials for oil spill cleanup and wastewater treatment. The novelty of this work lies in its dual modification approach—PTFE decoration for hydrophobicity and metal doping for enhanced adsorption—demonstrating a tunable strategy for optimizing COF surfaces in environmental applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115202"},"PeriodicalIF":3.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143760723","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":"A comparative density functional theory (DFT) and molecular dynamics study on Natamycin and Cefmetazole as effective corrosion inhibitor for mild steel: Electronic properties and adsorption behavior","authors":"Fidelis E. Abeng ,&nbsp;Abhinay Thakur ,&nbsp;Valentine Chikaodili Anadebe ,&nbsp;Eno E. Ebenso","doi":"10.1016/j.comptc.2025.115200","DOIUrl":"10.1016/j.comptc.2025.115200","url":null,"abstract":"<div><div>This work investigated the corrosion inhibition mechanism of Natamycin and Cefmetazole on mild steel using Density Functional Theory (DFT) and Molecular Dynamic (MD) simulation. Natamycin exhibited a low HOMO-LUMO energy gap of 0.5 eV and a high adsorption energy of −92.7 kJ/mol which demonstrates its high chemical reactivity for effective adsorption on metal surfaces. The presence of hydroxyl groups and conjugated double bonds in its structure allows for fast electron exchange to generate strongly adhesive protective films. Cefmetazole with HOMO-LUMO gap of 2.45 eV and adsorption energy of −67 kJ/mol with β-lactam and sulfur on the adsorbent surface providing strong hydrogen bonding with the metal atoms. The independence of the generated geometries is additionally supported through MD simulations showing their adsorption configurations when providing the optimal spreading and orientation to block corrosive agents. Natamycin reacted more readily and adsorbed spontaneously, showing its suitability for use in acidic media, whereas, Cefmetazole, in contrast, affords an even inhibition profile, though only of moderate chemical stability. The conclusions also show dispositions of pharmaceutical compounds that may be used as green corrosion inhibitors which comply with the green chemistry roadmap.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115200"},"PeriodicalIF":3.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143705492","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":"Hydrogen storage capacities of first-row transition-metal modified phosphorene: A computational study","authors":"Cesar Gabriel Vera-de la Garza,&nbsp;Daniela Osorio Sandoval,&nbsp;Wilmer Esteban Vallejo Narváez,&nbsp;Serguei Fomine","doi":"10.1016/j.comptc.2025.115210","DOIUrl":"10.1016/j.comptc.2025.115210","url":null,"abstract":"","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115210"},"PeriodicalIF":3.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726220","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":"Dopant-free hole transport materials for perovskite solar cells and donor molecules for organic solar cells","authors":"Zeeshana Bibi ,&nbsp;Javed Iqbal ,&nbsp;Ali Raza Ayub ,&nbsp;Amna Ayub ,&nbsp;Sehrish Gul","doi":"10.1016/j.comptc.2025.115199","DOIUrl":"10.1016/j.comptc.2025.115199","url":null,"abstract":"<div><div>This work aimed to create new Ullazine derivatives as hole-transporting materials (HTMs) for perovskite solar cells (PSCs) and donor materials for organic solar cells (OSCs). The newly devised compounds <strong>(UM1-UM6)</strong> exhibit much smaller energy band gaps and a broader λ_max than the <strong>UMR</strong> because of their strong electron-attracting groups. While <strong>UMR</strong> has a bandgap of 3.37 eV, the produced molecules ranged from 1.45 to 2.08 eV. The λ_max of <strong>UM1-UM6</strong> in DCM are 376–460 nm, while the λ_max value of <strong>UMR</strong> is 408 nm. The reference <strong>UMR</strong> has a λ_h value of 0.008164 eV, whereas the computationally computed λ_h values of the <strong>UM1-UM6</strong> created molecules range from 0.003777 to 0.008791 eV. Reason being, the acceptor moieties of these compounds make hole transit easier. Furthermore, after all of the newly created molecules were scaled with a PC₆₁BM acceptor, the Voc values were comparable to or higher than the reference, suggesting that these molecules are in a good position to increase efficiency. In terms of PCE (6.27 to 12.33 %), the newly created compounds <strong>(UM1-UM6)</strong> perform better than the reference compound (PCE = 7.80 %). The newly designed compounds <strong>(UM1-UM6)</strong> have the potential to be used as noble HTMs in the development of more advanced perovskite solar cells (PSCs) and donor molecules for organic solar cells (OSCs) in the future.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115199"},"PeriodicalIF":3.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726215","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":"A theoretical study of the effect of end-group and center backbone modifications on the optoelectronic properties of Y6-based asymmetric LL3 non-fullerene","authors":"Liu Yang,&nbsp;Yunjie Xiang,&nbsp;Shaohui Zheng","doi":"10.1016/j.comptc.2025.115208","DOIUrl":"10.1016/j.comptc.2025.115208","url":null,"abstract":"<div><div>Y6-based non-fullerene acceptor (NFA) has garnered significant attention because of its unique A-DA'D-A molecular structure. However, the impact of asymmetric modification—a key strategy to enhance NFAs—on their photovoltaic properties is still not well understood. In this study, we optimized the high-performance asymmetric LL3, a Y6-based NFA characterized by its distinctive 3D end-group structure, by employing end-group and skeleton modification techniques. We designed six new asymmetric NFA candidates by expanding thiophene rings within the skeleton's core, incorporating π-bridges, and substituting chlorinated benzene rings or 3D segments at the end-groups with thiophene. Using density functional theory (DFT) and time-dependent DFT (TD-DFT), we calculated various molecular properties of these NFAs, such as molecular planarity, dipole moments, frontier molecular orbitals, electrostatic potential (ESP), electron-hole distributions, UV–Visible absorption spectra, singlet-triplet energy difference (ΔE_ST), exciton binding energy (E_b), and the open circuit voltages of organic solar cells based on these NFAs. Our results show that five of the new NFAs outperform the prototype LL3, with LL3-T-L standing out due to its red-shifted absorption peak, highest light absorption intensity, lower ΔE_ST and E_b, and enhanced ESP, indicating its potential as a high-performance NFA. These findings provide theoretical guidance for future experimental synthesis and device optimization.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115208"},"PeriodicalIF":3.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143715743","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":"Modeling electronic structure and charge transport properties of Tetrathienopyrrole-based hole-transporting materials: A DFT approach for enhanced photovoltaic efficiency towards efficient perovskite solar cells","authors":"Rida Fatima ,&nbsp;Nabeel Shahzad ,&nbsp;Mahwish Iqbal ,&nbsp;Tahreem Fatima ,&nbsp;Shaimaa A.M. Abdelmohsen ,&nbsp;Javed Iqbal","doi":"10.1016/j.comptc.2025.115204","DOIUrl":"10.1016/j.comptc.2025.115204","url":null,"abstract":"<div><div>This quantum mechanical approach paved the way for fabricating highly stable hole-transporting materials for photovoltaic cells. This scheme involved the integration of acceptor terminal units through a thiophene spacer to the versatile symmetrical tetrathienopyrrole core connected to dimethoxytriphenylamine helix units, resulting in a series of six novel HTMs (DTT-1 to DTT-6). Comprehensive analysis of the energetics of energy levels (HOMO/LUMO), solvation energy, density of states (DOS), and stability of proposed HTMs were evaluated by systematically performing the quantum computation via (DFT) and (TD-DFT). The results revealed that fabricated HTMs (DTT-1 to DTT-6 unveiled stabilized HOMO levels approaching the edge with suitable HTM/perovskite energy level alignment, proposing exceptional charge extraction and high open circuit voltage. Photophysical analysis indicated that our fabricated HTMs revealed larger Stokes shift values (75 nm −150 nm) and transparency in the visible region, allowing full utilization of sunlight for the perovskite layer for photocurrent generation and enhanced spectral selectivity. The proposed HTMs showed smaller RE values ranging from 0.106 eV to 0.23 eV and greater transfer integral, signifying ultrafast hole mobility. Moreover, comparatively higher dipole moments (2.81 D-11.07 D) and higher negative solvation energies (−18.62 kcal/mol to −21.86 kcal/mol) suggested improved solubility and film-forming attributes. Hence, this study provides crucial insights into the deliberate and effective design of high-performance HTMs.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115204"},"PeriodicalIF":3.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143716147","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":"Rational design and DFT-based study of non-fullerene acceptors for high-performance organic solar cells: End-cap and Core modifications for enhanced charge transfer","authors":"Adeel Mubarik,&nbsp;Faiza Shafiq,&nbsp;Xue-Hai Ju","doi":"10.1016/j.comptc.2025.115209","DOIUrl":"10.1016/j.comptc.2025.115209","url":null,"abstract":"<div><div>In this article, we reported the 64 newly designed non-fullerene acceptors (NFAs) using density functional theory (DFT) approaches combined with both central core and end-cap modification. We screened out five promising molecules among 64 molecules using four specific criteria and their structural as well as optoelectronic attributes were calculated. Using DFT techniques, we thoroughly examined the optical, electrical, and excited state characteristics such as energy gap, maximum absorption, excitation energy (<em>E</em>_<em>x</em>), and oscillator strength to evaluate the effects of various end-cap groups on different core architectures. Furthermore, we paired the most promising NFAs with the P3HT polymer donor to generate donor-acceptor interfaces, and we examined the open circuit voltage (<em>V</em>_<em>oc</em>) and rate of charge transfer (CT) at these interfaces. The conclusions offer insightful advice and useful design guidelines for high-performance NFAs that have the potential to greatly increase solar devices' efficiency.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115209"},"PeriodicalIF":3.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726216","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":"First-principles study on single-layer electronic structure of Fe-doped MoS2 and the reduction of NO on the doped surface","authors":"Xiangzhen Xiao ,&nbsp;Yinli Cao ,&nbsp;Linfeng Hu","doi":"10.1016/j.comptc.2025.115172","DOIUrl":"10.1016/j.comptc.2025.115172","url":null,"abstract":"<div><div>Electrocatalytic reduction represents an effective approach for the conversion of the harmful gas nitric oxide (NO) into ammonia (NH₃), a vital chemical precursor in industrial production. However, the large-scale practical application of NO electrocatalytic reduction remains a significant challenge, particularly in the identification of efficient, low-cost, and stable catalysts. In this study, we investigate the electronic structure, magnetic properties, and stability of the Fe-MoS₂ doping system using first-principles calculations. We explore the activation mechanism of NO molecules by Fe-MoS₂ and assess its potential as an electrocatalyst for NO reduction by examining the electronic structure of the adsorbed states. Our results show that Fe doping effectively modulates the electronic structure of MoS₂, significantly enhancing its capacity to adsorb NO compared to pristine molybdenum disulfide surfaces. Analysis of charge transfer and electronic properties during NO adsorption reveals a charge transfer of 0.32e between the substrate and the adsorbed NO molecule. Furthermore, the 2p<span><math><msub><mrow></mrow><mrow><mi>y</mi></mrow></msub></math></span> and 2p<span><math><msub><mrow></mrow><mrow><mi>x</mi></mrow></msub></math></span> orbitals of the nitrogen atom exhibit partial overlap with the 3d<span><math><msub><mrow></mrow><mrow><mi>xy</mi></mrow></msub></math></span>, 3d<span><math><msub><mrow></mrow><mrow><mi>yz</mi></mrow></msub></math></span>, and 3d<span><math><msub><mrow></mrow><mrow><mi>xz</mi></mrow></msub></math></span> orbitals of the Fe atom near the Fermi level, indicating strong interactions that facilitate NO activation. The hydrogenation process of NO to ammonia was further investigated using two different approaches. The results demonstrated the exceptional electrocatalytic reduction activity of Fe-doped S vacancy towards NO. This study not only provides a concise depiction of the Fe-MoS₂ electrocatalyst but also verifies the feasibility of utilizing Fe-MoS₂ for the electrocatalytic synthesis of ammonia from NO.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115172"},"PeriodicalIF":3.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143705491","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":"Theoretical study of catalytic performance of X-γ-Graphyne as cathodes for lithium-air batteries","authors":"Armando Vera-Garcia ,&nbsp;J.H. Pacheco-Sanchez ,&nbsp;Frank J. Isidro-Ortega ,&nbsp;Abraham González-Ruíz ,&nbsp;J.S. Arellano","doi":"10.1016/j.comptc.2025.115197","DOIUrl":"10.1016/j.comptc.2025.115197","url":null,"abstract":"<div><div>Lithium-air batteries (Li<img>O₂) are considered one of the most promising energy storage and conversion device candidates for future mobility applications, such as electric vehicles, due to their ultrahigh theoretical energy density (up to ∼3600 Wh kg^‐1). The main goal in this work is to study an electrochemical catalytic model for a cathode in Li<img>O₂ batteries to simulate the OER during the discharging process. Density Functional Theory (DFT) calculations were performed to investigate γ-Graphyne and N-γ-Graphyne (N-Doped γ-Graphyne) as the potential cathode catalyst for Li<img>O₂ batteries. γ-Graphyne and N-γ-Graphyne surfaces exhibit high stability according to calculations, the pristine surface exhibits a slight improvement in the formation energy of Li_xO₂, moreover, the N-Doped surface can reduce the significant formation energy of Li_xO₂ in the OER. Calculations explain the catalytic mechanism and identify the active sites to perform N-doping on pristine γ-Graphyne. This study demonstrates a feasible approach to achieve designed γ-Graphyne and N-γ-Graphyne as cathode catalysts for Li air batteries, which is promising for cost reduction in mass production of Li-air batteries.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115197"},"PeriodicalIF":3.0,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726219","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}