Pub Date : 2025-03-27DOI: 10.1016/j.comptc.2025.115205
Shengfengrui Zhang , Changqing Lin , Binyuan Huang , Yang Xue , Dan Huang
Chalcopyrite compounds are employed as host materials for intermediate band solar cells owing to the wide band gaps and excellent optical properties. In this study, we focus on the chalcopyrite AgGaS2 as a potential host for intermediate band solar cell. To identify an ideal absorber for an intermediate band solar cell, the structural stability, electronic structure, and the possibility of achieving of the large doping concentration are investigated on group-IV element (Si, Ge, Sn) doped AgGaS2 using the first-principles calculations. Based on the ab-initio molecular dynamic simulation and the calculations on the phonon spectrum, the doped samples exhibited strong dynamic stabilities and thermodynamic stabilities. The calculations on electronic structures indicate that Ge and Sn doped at Ga site can form isolated and partially filled intermediate bands in AgGaS2, whereas Si doped at Ga site cannot. In addition, the feasibility of large doping concentration is investigated, and the results show that the lowest defect formation energy is obtained for Sn doping at Ga site under Ag-poor, Ga-poor and S-rich conditions. Overall, our theoretical work suggested that Sn doped AgGaS2 is an ideal absorber for the intermediate band solar cell.
{"title":"A theoretical study on absorbers for the intermediate band solar cell from group-IV element (Si, Ge, Sn) doped AgGaS2","authors":"Shengfengrui Zhang , Changqing Lin , Binyuan Huang , Yang Xue , Dan Huang","doi":"10.1016/j.comptc.2025.115205","DOIUrl":"10.1016/j.comptc.2025.115205","url":null,"abstract":"<div><div>Chalcopyrite compounds are employed as host materials for intermediate band solar cells owing to the wide band gaps and excellent optical properties. In this study, we focus on the chalcopyrite AgGaS<sub>2</sub> as a potential host for intermediate band solar cell. To identify an ideal absorber for an intermediate band solar cell, the structural stability, electronic structure, and the possibility of achieving of the large doping concentration are investigated on group-IV element (Si, Ge, Sn) doped AgGaS<sub>2</sub> using the first-principles calculations. Based on the <em>ab-initio</em> molecular dynamic simulation and the calculations on the phonon spectrum, the doped samples exhibited strong dynamic stabilities and thermodynamic stabilities. The calculations on electronic structures indicate that Ge and Sn doped at Ga site can form isolated and partially filled intermediate bands in AgGaS<sub>2</sub>, whereas Si doped at Ga site cannot. In addition, the feasibility of large doping concentration is investigated, and the results show that the lowest defect formation energy is obtained for Sn doping at Ga site under Ag-poor, Ga-poor and S-rich conditions. Overall, our theoretical work suggested that Sn doped AgGaS<sub>2</sub> is an ideal absorber for the intermediate band solar cell.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115205"},"PeriodicalIF":3.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726217","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}
Pub Date : 2025-03-27DOI: 10.1016/j.comptc.2025.115211
Corinna Lombardo, Giulia Varrica, Giuseppe Forte
The escalating use of heavy metals in industrial, agricultural, and medical applications has amplified pollution challenges, necessitating innovative remediation strategies. This study investigates the potential of a hybrid graphene oxide/thiolated-poly(N-isopropylacrylamide) (GO/GOSH@PNM) system for the reversible, temperature-dependent removal of heavy metals, specifically Pd(II), Pb(II), and Cd(II), from aqueous environments. Molecular dynamics (MD) simulations reveal that below the lower critical solution temperature (LCST) of 32 °C, the PNM polymer adopts a hydrophilic coil configuration, enabling efficient coordination of metal cations via hydroxyl, thiol, and amide oxygen functional groups. Density functional theory (DFT) calculations corroborate these findings, highlighting favorable adsorption free energies and strong interactions between the polymer and metal ions at lower temperatures. Above 32 °C, the polymer transitions to a hydrophobic globular conformation, reducing cation affinity and facilitating their release. This temperature-induced binding and release mechanism allows for heavy metal recovery and the regeneration of the hybrid system. The GO surface demonstrates higher polymer affinity than the GOSH surface, likely due to its increased hydroxyl group density. These findings underline the potential of the GO/GOSH@PNM system for sustainable and efficient heavy metal remediation, with further optimization promising enhanced performance.
{"title":"Computational study on thiolated and functionalized graphene oxide for heavy metal recovery","authors":"Corinna Lombardo, Giulia Varrica, Giuseppe Forte","doi":"10.1016/j.comptc.2025.115211","DOIUrl":"10.1016/j.comptc.2025.115211","url":null,"abstract":"<div><div>The escalating use of heavy metals in industrial, agricultural, and medical applications has amplified pollution challenges, necessitating innovative remediation strategies. This study investigates the potential of a hybrid graphene oxide/thiolated-poly(N-isopropylacrylamide) (GO/GOSH@PNM) system for the reversible, temperature-dependent removal of heavy metals, specifically Pd(II), Pb(II), and Cd(II), from aqueous environments. Molecular dynamics (MD) simulations reveal that below the lower critical solution temperature (LCST) of 32 °C, the PNM polymer adopts a hydrophilic coil configuration, enabling efficient coordination of metal cations via hydroxyl, thiol, and amide oxygen functional groups. Density functional theory (DFT) calculations corroborate these findings, highlighting favorable adsorption free energies and strong interactions between the polymer and metal ions at lower temperatures. Above 32 °C, the polymer transitions to a hydrophobic globular conformation, reducing cation affinity and facilitating their release. This temperature-induced binding and release mechanism allows for heavy metal recovery and the regeneration of the hybrid system. The GO surface demonstrates higher polymer affinity than the GOSH surface, likely due to its increased hydroxyl group density. These findings underline the potential of the GO/GOSH@PNM system for sustainable and efficient heavy metal remediation, with further optimization promising enhanced performance.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115211"},"PeriodicalIF":3.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739935","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}
Pub Date : 2025-03-26DOI: 10.1016/j.comptc.2025.115201
Kieu Van T. Nguyen , Khung M. Trang , Tam T.-V. Mai , Quan Phung , Phuong Hoang Tran , Yoshiyuki Kawazoe , Nguyen Nguyen T. Pham
The Friedel-Crafts acylation of indole with propionic anhydride using a metal-triflate catalyst is an efficient and environmentally friendly method for synthesizing 3-acylindole, an important pharmaceutical intermediate. Despite its high selectivity for the C-3 position without requiring NH protection, the exact mechanism by which the metal-triflate catalyst promotes regioselective acylation remains unclear. In this study, density functional theory (DFT) calculations were employed to explore acyl substitution at three positions on the indole ring, both in the presence and absence of the catalyst. Two possible mechanisms were proposed: (i) an indirect pathway, where the catalyst forms an electrophilic intermediate (PrOTf) to acylate indole, and (ii) a direct pathway, where indole reacts directly with propionic anhydride at the metal core. The results indicated that the indirect pathway favored N-acylation, while the direct pathway preferred 3-acylindole. Both pathways were observed across several metal triflate catalysts (M = Y, In, Bi, La), in line with experimental data.
{"title":"DFT – Proposed mechanism of Friedel–Crafts acylation of indole using metal triflate catalysts","authors":"Kieu Van T. Nguyen , Khung M. Trang , Tam T.-V. Mai , Quan Phung , Phuong Hoang Tran , Yoshiyuki Kawazoe , Nguyen Nguyen T. Pham","doi":"10.1016/j.comptc.2025.115201","DOIUrl":"10.1016/j.comptc.2025.115201","url":null,"abstract":"<div><div>The Friedel-Crafts acylation of indole with propionic anhydride using a metal-triflate catalyst is an efficient and environmentally friendly method for synthesizing 3-acylindole, an important pharmaceutical intermediate. Despite its high selectivity for the C-3 position without requiring NH protection, the exact mechanism by which the metal-triflate catalyst promotes regioselective acylation remains unclear. In this study, density functional theory (DFT) calculations were employed to explore acyl substitution at three positions on the indole ring, both in the presence and absence of the catalyst. Two possible mechanisms were proposed: (<em>i</em>) an indirect pathway, where the catalyst forms an electrophilic intermediate (PrOTf) to acylate indole, and (<em>ii</em>) a direct pathway, where indole reacts directly with propionic anhydride at the metal core. The results indicated that the indirect pathway favored N-acylation, while the direct pathway preferred 3-acylindole. Both pathways were observed across several metal triflate catalysts (M = Y, In, Bi, La), in line with experimental data.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115201"},"PeriodicalIF":3.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143769333","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}
Pub Date : 2025-03-26DOI: 10.1016/j.comptc.2025.115215
Lixin Ye, Jiake Fan, Lei Yang, Mengyun Mei, Zijian Sun, Hui Li, Weihua Zhu
Nitrogen oxide reduction reaction (NORR) is a highly efficient method for reducing NO to synthesize ammonia. Herein, we designed 18 transition-metal (TM)-doped phthalocyanine materials and combined density functional theory (DFT) with machine learning (ML) to systematically study their catalytic performance for NORR through comprehensive evaluations of their NO adsorption energy, electronic structure, and Gibbs free energy. Our results indicate that NO can adsorb on V1@Pc with a moderate adsorption energy (−2.29 eV) and the lowest limiting potential (0.38 V) among the 18 TM1@Pc materials. Additionally, V1@Pc can effectively mitigate the competitive hydrogen evolution reaction (HER), showing that it has a remarkable performance of efficiency and selectivity for NORR. Finally, machine learning techniques were employed to construct predictive models by utilizing key feature descriptors derived from DFT calculations and intrinsic atomic properties. Among the five regression models, the Random Forest Regression (RFR) exhibits the highest accuracy (R2 = 0.99) and the lowest RMSE (0.15 eV) in predicting Gibbs free energy. Our study may provide valuable theoretical insights for the rational design of high-performance electrocatalysts for NORR.
氧化氮还原反应（NORR）是还原 NO 合成氨的一种高效方法。在此，我们设计了 18 种过渡金属（TM）掺杂的酞菁材料，并将密度泛函理论（DFT）与机器学习（ML）相结合，通过对其 NO 吸附能、电子结构和吉布斯自由能的综合评估，系统地研究了它们在 NORR 中的催化性能。我们的研究结果表明，在 18 种 TM1@Pc 材料中，NO 能以中等吸附能（-2.29 eV）和最低极限电位（0.38 V）吸附在 V1@Pc 上。此外，V1@Pc 还能有效缓解竞争性氢进化反应（HER），表明其在 NORR 的效率和选择性方面具有显著的性能。最后，研究人员采用机器学习技术，利用从 DFT 计算和内在原子特性中得出的关键特征描述符构建了预测模型。在五个回归模型中，随机森林回归（RFR）预测吉布斯自由能的准确度最高（R2 = 0.99），RMSE 最低（0.15 eV）。我们的研究可为合理设计用于 NORR 的高性能电催化剂提供有价值的理论启示。
{"title":"Accelerating design of phthalocyanine-based catalysts for electrocatalytic reduction of nitric oxide: A DFT and machine learning study","authors":"Lixin Ye, Jiake Fan, Lei Yang, Mengyun Mei, Zijian Sun, Hui Li, Weihua Zhu","doi":"10.1016/j.comptc.2025.115215","DOIUrl":"10.1016/j.comptc.2025.115215","url":null,"abstract":"<div><div>Nitrogen oxide reduction reaction (NORR) is a highly efficient method for reducing NO to synthesize ammonia. Herein, we designed 18 transition-metal (TM)-doped phthalocyanine materials and combined density functional theory (DFT) with machine learning (ML) to systematically study their catalytic performance for NORR through comprehensive evaluations of their NO adsorption energy, electronic structure, and Gibbs free energy. Our results indicate that NO can adsorb on V1@Pc with a moderate adsorption energy (−2.29 eV) and the lowest limiting potential (0.38 V) among the 18 TM1@Pc materials. Additionally, V1@Pc can effectively mitigate the competitive hydrogen evolution reaction (HER), showing that it has a remarkable performance of efficiency and selectivity for NORR. Finally, machine learning techniques were employed to construct predictive models by utilizing key feature descriptors derived from DFT calculations and intrinsic atomic properties. Among the five regression models, the Random Forest Regression (RFR) exhibits the highest accuracy (R<sup>2</sup> = 0.99) and the lowest RMSE (0.15 eV) in predicting Gibbs free energy. Our study may provide valuable theoretical insights for the rational design of high-performance electrocatalysts for NORR.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115215"},"PeriodicalIF":3.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739934","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}
Pub Date : 2025-03-26DOI: 10.1016/j.comptc.2025.115207
C. Ragi, K. Muraleedharan
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 (>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.
{"title":"A theoretical evaluation of the multiple radical scavenging reactions of Hibiscetin","authors":"C. Ragi, 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 (>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}
Pub Date : 2025-03-25DOI: 10.1016/j.comptc.2025.115202
Bassey E. Inah , N. Favour Azogor , Hannah Tom Akpan , Okereke E. Levi , Destiny Charlie , Adebayo P. Adeleye
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.
{"title":"Exploring the adsorption properties of PTFE-decorated and metal doped covalent organic frameworks for environmental cleanup: A computational outlook","authors":"Bassey E. Inah , N. Favour Azogor , Hannah Tom Akpan , Okereke E. Levi , Destiny Charlie , 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 × 10<sup>13</sup> A/m<sup>2</sup>) 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}
Pub Date : 2025-03-25DOI: 10.1016/j.comptc.2025.115200
Fidelis E. Abeng , Abhinay Thakur , Valentine Chikaodili Anadebe , Eno E. Ebenso
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.
{"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 , Abhinay Thakur , Valentine Chikaodili Anadebe , 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}
Pub Date : 2025-03-25DOI: 10.1016/j.comptc.2025.115199
Zeeshana Bibi , Javed Iqbal , Ali Raza Ayub , Amna Ayub , Sehrish Gul
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 (UM1-UM6) exhibit much smaller energy band gaps and a broader λmax than the UMR because of their strong electron-attracting groups. While UMR has a bandgap of 3.37 eV, the produced molecules ranged from 1.45 to 2.08 eV. The λmax of UM1-UM6 in DCM are 376–460 nm, while the λmax value of UMR is 408 nm. The reference UMR has a λh value of 0.008164 eV, whereas the computationally computed λh values of the UM1-UM6 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 (UM1-UM6) perform better than the reference compound (PCE = 7.80 %). The newly designed compounds (UM1-UM6) 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.
{"title":"Dopant-free hole transport materials for perovskite solar cells and donor molecules for organic solar cells","authors":"Zeeshana Bibi , Javed Iqbal , Ali Raza Ayub , Amna Ayub , 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<sub>max</sub> 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<sub>max</sub> of <strong>UM1-UM6</strong> in DCM are 376–460 nm, while the λ<sub>max</sub> value of <strong>UMR</strong> is 408 nm. The reference <strong>UMR</strong> has a λ<sub>h</sub> value of 0.008164 eV, whereas the computationally computed λ<sub>h</sub> 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 PC<sub>61</sub>BM 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}
Pub Date : 2025-03-25DOI: 10.1016/j.comptc.2025.115208
Liu Yang, Yunjie Xiang, Shaohui Zheng
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 (ΔEST), exciton binding energy (Eb), 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 ΔEST and Eb, and enhanced ESP, indicating its potential as a high-performance NFA. These findings provide theoretical guidance for future experimental synthesis and device optimization.
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