We have computationally designed nine diarylmethyl diradicals to understand the increasing trend of magnetic exchange coupling constant with the cumulene length. We have computed the magnetic exchange coupling constant with four different DFT functionals namely B3LYP, MN12SX, M06L and BP86 to check the consistency of the results. The molecular orbital analysis and their energy gap have also been studied. The bond length alternation increases with an increase in the length of the coupler. This suggests a clear shift in the molecule's electronic distribution with the increase in the cumulene length due to the interaction of the radical centers and the cumulene. All the functionals give consistent ferromagnetic interactions for the designed diradicals. After a certain length of the cumulene coupler the magnetic exchange coupling constant of the diradicals reached a saturation point. The MO analysis shows that the saturation of magnetic exchange comes from the reduced helical nature of LUMO.
{"title":"Saturation of magnetic exchange coupling with increasing cumulene coupler length in diarylmethyl diradicals","authors":"Muskan , Chumuiria Debbarma , Anirban Misra , Suranjan Shil","doi":"10.1016/j.comptc.2025.115631","DOIUrl":"10.1016/j.comptc.2025.115631","url":null,"abstract":"<div><div>We have computationally designed nine diarylmethyl diradicals to understand the increasing trend of magnetic exchange coupling constant with the cumulene length. We have computed the magnetic exchange coupling constant with four different DFT functionals namely B3LYP, MN12SX, M06L and BP86 to check the consistency of the results. The molecular orbital analysis and their energy gap have also been studied. The bond length alternation increases with an increase in the length of the coupler. This suggests a clear shift in the molecule's electronic distribution with the increase in the cumulene length due to the interaction of the radical centers and the cumulene. All the functionals give consistent ferromagnetic interactions for the designed diradicals. After a certain length of the cumulene coupler the magnetic exchange coupling constant of the diradicals reached a saturation point. The MO analysis shows that the saturation of magnetic exchange comes from the reduced helical nature of LUMO.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115631"},"PeriodicalIF":3.0,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796688","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 : 2025-12-09DOI: 10.1016/j.comptc.2025.115630
Haipeng Chen , Wenran Meng , Yiming Li , Shuwen Hou , Minjian Yang , Pei Liu , Baozhong Liu
Nano-Mg-based hydrogen storage materials exhibit superior hydrogen storage performance, but their poor safety hinder practical applications. A promising strategy to improve the safety of these materials involves constructing a nonmetallic heteroatom passivation layer on nano-Mg surface through small molecules dissociation. Herein, first-principles calculation was employed to study the adsorption and dissociation of CH4, NH3, H2O, and H2S molecules on Mg(0001), as well as to clarify the effect of the passivation layer on hydrogen diffusion. The introduction of heteroatom enhances small molecules adsorption through strengthened orbital hybridization between H and Mg atoms. Increasing heteroatom coverage reduces the density of states near the Fermi level, lowers surface energy, and improves surface stability, consequently increasing the dissociation energy barriers of small molecules and increasing the diffusion energy barriers of hydrogen. H2S emerges as the ideal option for constructing a passivation layer because it can readily form a passivation layer and effectively balance safety and hydrogen diffusion. This study can provide valuable insights for designing nano-Mg-based hydrogen storage materials with optimized safety and thermodynamic properties.
{"title":"Tuning surface stability and hydrogen diffusion on nano magnesium surface via nonmetallic heteroatom functionalization: A first-principles study","authors":"Haipeng Chen , Wenran Meng , Yiming Li , Shuwen Hou , Minjian Yang , Pei Liu , Baozhong Liu","doi":"10.1016/j.comptc.2025.115630","DOIUrl":"10.1016/j.comptc.2025.115630","url":null,"abstract":"<div><div>Nano-Mg-based hydrogen storage materials exhibit superior hydrogen storage performance, but their poor safety hinder practical applications. A promising strategy to improve the safety of these materials involves constructing a nonmetallic heteroatom passivation layer on nano-Mg surface through small molecules dissociation. Herein, first-principles calculation was employed to study the adsorption and dissociation of CH<sub>4</sub>, NH<sub>3</sub>, H<sub>2</sub>O, and H<sub>2</sub>S molecules on Mg(0001), as well as to clarify the effect of the passivation layer on hydrogen diffusion. The introduction of heteroatom enhances small molecules adsorption through strengthened orbital hybridization between H and Mg atoms. Increasing heteroatom coverage reduces the density of states near the Fermi level, lowers surface energy, and improves surface stability, consequently increasing the dissociation energy barriers of small molecules and increasing the diffusion energy barriers of hydrogen. H<sub>2</sub>S emerges as the ideal option for constructing a passivation layer because it can readily form a passivation layer and effectively balance safety and hydrogen diffusion. This study can provide valuable insights for designing nano-Mg-based hydrogen storage materials with optimized safety and thermodynamic properties.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115630"},"PeriodicalIF":3.0,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748299","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 : 2025-12-08DOI: 10.1016/j.comptc.2025.115625
S. Vijayalakshmi, V. Vijayapriya, M. Devibala, M. Sowmiya, M. Hema
The hydrogen storage capacity analysis is done for the silicene polymorphs of low buckled silicene (LBS), trigonal dumbbell shaped silicene (TDS), honeycomb dumbbell shaped silicene (HDS) and large honeycomb dumbbell shaped silicene (LHDS). The 2 × 1 × 1 supercell of LBS, TDS, HDS, and LHDS are modelled and the hydrogen adsorption energy calculation is done. The physisorption and chemisorption analysis is made based on the adsorption energy calculation and the need of metal decoration is identified. Since none of the polymorphs exhibits physisorption Li decoration was done for the adsorption of H2. It is found from the adsorption energy calculation that only the Li- decorated TDS alone favours the physisorption. From the electronic property analysis, it is interestingly to note that the physisorbed Li-decorated TDS exhibit the metallic behaviour whereas mon-physisorbed systems exhibit semiconducting behaviour with increased bandgaps upon hydrogenation.
{"title":"Investigation of hydrogen storage capacity in 2D silicene polymorphs through physisorption and metal decoration – a first-principles study","authors":"S. Vijayalakshmi, V. Vijayapriya, M. Devibala, M. Sowmiya, M. Hema","doi":"10.1016/j.comptc.2025.115625","DOIUrl":"10.1016/j.comptc.2025.115625","url":null,"abstract":"<div><div>The hydrogen storage capacity analysis is done for the silicene polymorphs of low buckled silicene (LBS), trigonal dumbbell shaped silicene (TDS), honeycomb dumbbell shaped silicene (HDS) and large honeycomb dumbbell shaped silicene (LHDS). The 2 × 1 × 1 supercell of LBS, TDS, HDS, and LHDS are modelled and the hydrogen adsorption energy calculation is done. The physisorption and chemisorption analysis is made based on the adsorption energy calculation and the need of metal decoration is identified. Since none of the polymorphs exhibits physisorption Li decoration was done for the adsorption of H<sub>2</sub>. It is found from the adsorption energy calculation that only the Li- decorated TDS alone favours the physisorption. From the electronic property analysis, it is interestingly to note that the physisorbed Li-decorated TDS exhibit the metallic behaviour whereas mon-physisorbed systems exhibit semiconducting behaviour with increased bandgaps upon hydrogenation.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115625"},"PeriodicalIF":3.0,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145747791","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 : 2025-12-08DOI: 10.1016/j.comptc.2025.115628
Jinchao Qiao , Qiang Zhou , Fan Bai , Rufei Qiao , Zhuwen Lyu , Longhai Zhong , Junbo Yan , Peng Si
Two-dimensional (2D) black phosphorus (BP), as a representative layered van der Waals (vdW) material, exhibits unique polymorphic transitions under high pressure, which lays the foundation for its functional regulation. This study systematically investigates the mechanical, electronic, and bonding evolution mechanisms of high pressure phases (orthorhombic, rhombohedral, cubic) of 2D BP and their titanium (Ti)-doped systems through first principles calculations, aiming to fill the gap in the property modulation of 2D layered BP under extreme conditions. Using the VASP 6.4.3 platform, Ti-doped BP models with a Ti:P atomic ratio of 1:20 were constructed based on the three high pressure phases. Geometric optimization was performed via PAW pseudopotentials and PBE-GGA functionals, incorporating DFT-D3 corrections to accurately describe interlayer vdW interactions—an essential feature of layered 2D materials. Elastic constant calculations confirm that all Ti-doped high pressure phase structures satisfy the mechanical stability criteria of their respective crystal systems, with the cubic phase showing the most significant enhancement in Young's modulus (reaching 78.62 GPa after doping). Band structure analysis reveals phase dependent electronic reconstruction characteristics of this 2D layered system: Ti doping induces bandgap narrowing (from 0.82 eV to 0.70 eV) in the orthorhombic phase, a semimetal to metal transition in the rhombohedral phase, and optimized carrier mobility via sp3-d orbital hybridization in the cubic phase. Three-dimensional charge differential density reconstructions, combined with Bader charge analysis, further decode Ti-driven bonding evolution in the 2D lattice: strong covalent TiP bonds in the orthorhombic phase, distinct ionic characteristics in the rhombohedral phase, and dominant delocalized metallic bonds in the cubic phase. The established “doping-lattice symmetry-bonding” multiscale model for 2D BP provides theoretical guidance for tailoring the performance of BP-based 2D functional materials in high temperature electronic devices and flexible sensor systems
{"title":"First principles study on mechanical and electronic properties of high pressure phases of 2D black phosphorus and their titanium-doped systems","authors":"Jinchao Qiao , Qiang Zhou , Fan Bai , Rufei Qiao , Zhuwen Lyu , Longhai Zhong , Junbo Yan , Peng Si","doi":"10.1016/j.comptc.2025.115628","DOIUrl":"10.1016/j.comptc.2025.115628","url":null,"abstract":"<div><div>Two-dimensional (2D) black phosphorus (BP), as a representative layered van der Waals (vdW) material, exhibits unique polymorphic transitions under high pressure, which lays the foundation for its functional regulation. This study systematically investigates the mechanical, electronic, and bonding evolution mechanisms of high pressure phases (orthorhombic, rhombohedral, cubic) of 2D BP and their titanium (Ti)-doped systems through first principles calculations, aiming to fill the gap in the property modulation of 2D layered BP under extreme conditions. Using the VASP 6.4.3 platform, Ti-doped BP models with a Ti:P atomic ratio of 1:20 were constructed based on the three high pressure phases. Geometric optimization was performed via PAW pseudopotentials and PBE-GGA functionals, incorporating DFT-D3 corrections to accurately describe interlayer vdW interactions—an essential feature of layered 2D materials. Elastic constant calculations confirm that all Ti-doped high pressure phase structures satisfy the mechanical stability criteria of their respective crystal systems, with the cubic phase showing the most significant enhancement in Young's modulus (reaching 78.62 GPa after doping). Band structure analysis reveals phase dependent electronic reconstruction characteristics of this 2D layered system: Ti doping induces bandgap narrowing (from 0.82 eV to 0.70 eV) in the orthorhombic phase, a semimetal to metal transition in the rhombohedral phase, and optimized carrier mobility via sp<sup>3</sup>-d orbital hybridization in the cubic phase. Three-dimensional charge differential density reconstructions, combined with Bader charge analysis, further decode Ti-driven bonding evolution in the 2D lattice: strong covalent Ti<img>P bonds in the orthorhombic phase, distinct ionic characteristics in the rhombohedral phase, and dominant delocalized metallic bonds in the cubic phase. The established “doping-lattice symmetry-bonding” multiscale model for 2D BP provides theoretical guidance for tailoring the performance of BP-based 2D functional materials in high temperature electronic devices and flexible sensor systems</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115628"},"PeriodicalIF":3.0,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145747795","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 : 2025-12-05DOI: 10.1016/j.comptc.2025.115627
Shaoqiang Wei , Lei Li , Mengjiao Wu , Huanhuan Wu , Mengqi Yang , Min Zhang
Identifying the well-recognized active sites of single-atom catalysts to modulate the oxygen reduction reaction (ORR) catalytic activity and product selectivity is a challenging problem. In this work, using density functional theory (DFT) calculations, we conducted a systematic study for 3d metal and nitrogen co-doped graphene single-atom catalysts (MN4), as well as the MN4 modified by halogen ligand X (MN4–X). The results indicate that all catalysts, except for ZnN4 and ZnN4–X, are thermodynamically and electrochemically stable. The ORR follows the 4e− pathway on Cr/Mn/Fe/CoN4 and Cr/Mn/Fe/CoN4–X, while Ni/CuN4 and Ni/CuN4–X prefer the 2e− ORR pathway. The X ligand can effectively change the electronic structure of M active site to regulate the adsorption strength for reaction intermediates, thus enhancing the ORR catalytic activity. Notably, CoN4–Br/I have the lowest 4e− ORR overpotential of about 0.24 V and exhibit superior catalytic activity, significantly outperforming pure Pt catalysts. However, NiN4–F and CuN4 respectively with the overpotential of 0.08 and 0.03 V display the excellent 2e− ORR catalytic activity. Furthermore, the O2 adsorption energy, Bader charge transfer of M atoms, ΔG⁎OH, and ΔG⁎OOH were demonstrated to be the descriptors for evaluating the ORR activity and product selectivity. This study provides valuable insights for the design of highly efficient ORR catalysts.
{"title":"Engineering ORR electrocatalytic performance of single metal site by halogen ligand modification: A first principles perspective","authors":"Shaoqiang Wei , Lei Li , Mengjiao Wu , Huanhuan Wu , Mengqi Yang , Min Zhang","doi":"10.1016/j.comptc.2025.115627","DOIUrl":"10.1016/j.comptc.2025.115627","url":null,"abstract":"<div><div>Identifying the well-recognized active sites of single-atom catalysts to modulate the oxygen reduction reaction (ORR) catalytic activity and product selectivity is a challenging problem. In this work, using density functional theory (DFT) calculations, we conducted a systematic study for 3d metal and nitrogen co-doped graphene single-atom catalysts (MN<sub>4</sub>), as well as the MN<sub>4</sub> modified by halogen ligand X (MN<sub>4</sub>–X). The results indicate that all catalysts, except for ZnN<sub>4</sub> and ZnN<sub>4</sub>–X, are thermodynamically and electrochemically stable. The ORR follows the 4e<sup>−</sup> pathway on Cr/Mn/Fe/CoN<sub>4</sub> and Cr/Mn/Fe/CoN<sub>4</sub>–X, while Ni/CuN<sub>4</sub> and Ni/CuN<sub>4</sub>–X prefer the 2e<sup>−</sup> ORR pathway. The X ligand can effectively change the electronic structure of M active site to regulate the adsorption strength for reaction intermediates, thus enhancing the ORR catalytic activity. Notably, CoN<sub>4</sub>–Br/I have the lowest 4e<sup>−</sup> ORR overpotential of about 0.24 V and exhibit superior catalytic activity, significantly outperforming pure Pt catalysts. However, NiN<sub>4</sub>–F and CuN<sub>4</sub> respectively with the overpotential of 0.08 and 0.03 V display the excellent 2e<sup>−</sup> ORR catalytic activity. Furthermore, the O<sub>2</sub> adsorption energy, Bader charge transfer of M atoms, Δ<em>G</em><sub>⁎OH</sub>, and Δ<em>G</em><sub>⁎OOH</sub> were demonstrated to be the descriptors for evaluating the ORR activity and product selectivity. This study provides valuable insights for the design of highly efficient ORR catalysts.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115627"},"PeriodicalIF":3.0,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145747790","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 : 2025-12-04DOI: 10.1016/j.comptc.2025.115621
Abdelkrim Kessai , Nacir Guechi , Mustafa Kurban , Hakim Baaziz , Abdelhamid Layadi
We present a first-principles investigation, based on the pseudopotential plane-wave (PP-PW) method, of the CoMnTe/CdS(001) interfaces, focusing on the role of crystallographic site configurations—top (t), bridge (b), and hollow (h)—in determining their spintronic properties. These properties include structural stability, work function, half-metallicity, spin polarization, spin and charge populations, adhesion energy, and interfacial bonding. MnTe-terminated surface preserves the half-metallicity of bulk CoMnTe, while Co-terminated surface loses this feature due to created minority spin surface states (53 %) at the Fermi level (EF). Electronic and magnetic modifications are largely confined to the first two layers at the surface, where significant increase in Co and Mn magnetic moments are observed. Among twelve distinct interface configurations, only two—Co (b)/S and Mn (t)Te(h)/Cd—retain 100 % spin polarization at EF, with adhesion energies of 3.12 J/m2 and 0.51 J/m2, respectively. Hirshfeld charge and spin population analyses reveal covalent bonding between Co and S, and ionic bonding between Mn and Cd, along with a weak induced magnetic moment (−0.05 μB) on the Cd-terminated side. These findings identify promising interface configurations for spintronic device applications.
{"title":"Crystallographic site-dependent spintronic properties of CoMnTe/CdS(001) interfaces: A first-principles study","authors":"Abdelkrim Kessai , Nacir Guechi , Mustafa Kurban , Hakim Baaziz , Abdelhamid Layadi","doi":"10.1016/j.comptc.2025.115621","DOIUrl":"10.1016/j.comptc.2025.115621","url":null,"abstract":"<div><div>We present a first-principles investigation, based on the pseudopotential plane-wave (PP-PW) method, of the CoMnTe/CdS(001) interfaces, focusing on the role of crystallographic site configurations—top (t), bridge (b), and hollow (h)—in determining their spintronic properties. These properties include structural stability, work function, half-metallicity, spin polarization, spin and charge populations, adhesion energy, and interfacial bonding. MnTe-terminated surface preserves the half-metallicity of bulk CoMnTe, while Co-terminated surface loses this feature due to created minority spin surface states (53 %) at the Fermi level (<em>E</em><sub>F</sub>). Electronic and magnetic modifications are largely confined to the first two layers at the surface, where significant increase in Co and Mn magnetic moments are observed. Among twelve distinct interface configurations, only two—Co (b)/S and Mn (t)Te(h)/Cd—retain 100 % spin polarization at <em>E</em><sub>F</sub>, with adhesion energies of 3.12 J/m<sup>2</sup> and 0.51 J/m<sup>2</sup>, respectively. Hirshfeld charge and spin population analyses reveal covalent bonding between Co and S, and ionic bonding between Mn and Cd, along with a weak induced magnetic moment (−0.05 μ<sub>B</sub>) on the Cd-terminated side. These findings identify promising interface configurations for spintronic device applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115621"},"PeriodicalIF":3.0,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691224","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 : 2025-12-04DOI: 10.1016/j.comptc.2025.115626
Francisco Gleidson de S. Ferreira , Caio V.C. Ribeiro da Silva , Silvete Guerini , Kleuton A.L. Lima , Douglas Soares Galvão , José Milton Elias de Matos , Alexandre Araujo de Souza
The interaction of the pollutant chlorothalonil (CLT) with single-walled carbon nanotubes (CNTs) and boron nitride nanotubes (BNNTs) was investigated using density functional theory (DFT) calculations with the SIESTA software. Structural, energetic, and electronic properties were analyzed to characterize the effects of the interaction on the nanotube surfaces. Adsorption energy increases with increasing nanotube radius, attributed to enhanced π–π stacking interactions. The results indicate that both CNTs and BNNTs can physically adsorb CLT, but BNNTs are more promising candidates for CLT detection and removal in contaminated environments. Nanotube radius strongly affects all electronic and energetic properties. Molecular dynamics simulations performed in GROMACS confirmed the stability of CLT adsorbed on CNT and BNNT surfaces in aqueous solution.
{"title":"Effect of tube radius on the adsorption of chlorothalonil on single-walled carbon and boron nitride nanotubes surfaces: A theoretical study for environmental remediation","authors":"Francisco Gleidson de S. Ferreira , Caio V.C. Ribeiro da Silva , Silvete Guerini , Kleuton A.L. Lima , Douglas Soares Galvão , José Milton Elias de Matos , Alexandre Araujo de Souza","doi":"10.1016/j.comptc.2025.115626","DOIUrl":"10.1016/j.comptc.2025.115626","url":null,"abstract":"<div><div>The interaction of the pollutant chlorothalonil (CLT) with single-walled carbon nanotubes (CNTs) and boron nitride nanotubes (BNNTs) was investigated using density functional theory (DFT) calculations with the SIESTA software. Structural, energetic, and electronic properties were analyzed to characterize the effects of the interaction on the nanotube surfaces. Adsorption energy increases with increasing nanotube radius, attributed to enhanced π–π stacking interactions. The results indicate that both CNTs and BNNTs can physically adsorb CLT, but BNNTs are more promising candidates for CLT detection and removal in contaminated environments. Nanotube radius strongly affects all electronic and energetic properties. Molecular dynamics simulations performed in GROMACS confirmed the stability of CLT adsorbed on CNT and BNNT surfaces in aqueous solution.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115626"},"PeriodicalIF":3.0,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691226","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 : 2025-12-03DOI: 10.1016/j.comptc.2025.115622
Jinzhang Jia , Chaoyang Li , Peng Jia , Fengxiao Wang
To elucidate the wetting mechanisms of different functional groups at the molecular scale, this study systematically investigated the interaction mechanisms between 11 functional groups in coal and water using Density Functional Theory (DFT), Gran Canonica Monte Caro (GCMC), and Moecular Dynamics (MD) simulation methods. The study reveals that functional group polarity can be quantitatively distinguished by electrostatic potential maxima. As the sole bipolar functional group, the carboxyl group exhibits both strong donor and acceptor characteristics. It forms the strongest adsorption through C=O…H and O-H…O double hydrogen bonds, demonstrating superhydrophilicity. Front-line orbital analysis revealed that hydrophilic functional groups possess lower LUMO energy levels and higher electrophilic power, facilitating electron acceptance from water molecules. RDF analysis indicated that hydrophilic functional groups exhibit lower surface water molecule aggregation, promoting spreading. This study employs multiscale simulations to elucidate the mechanism by which functional groups influence coal wettability, providing precise theoretical foundations and design guidance for optimizing coal processing through surface functional group design.
为了在分子尺度上阐明不同官能团的润湿机理，本研究采用密度泛函理论（DFT）、Gran Canonica Monte Caro （GCMC）和分子动力学（MD）模拟方法系统研究了煤与水中11个官能团的相互作用机理。研究表明，可以通过静电势最大值定量地区分官能团极性。作为唯一的双极性官能团，羧基表现出强烈的供体和受体特征。通过C=O…H和O-H…O双氢键形成最强吸附，表现出超亲水性。前线轨道分析表明，亲水官能团具有较低的LUMO能级和较高的亲电能力，有利于从水分子中接受电子。RDF分析表明亲水性官能团表现出较低的地表水分子聚集，促进扩散。本研究通过多尺度模拟阐明了官能团对煤润湿性的影响机理，为通过表面官能团设计优化煤的加工提供了精确的理论依据和设计指导。
{"title":"Study on the influence of functional groups on coal surface wettability based on density functional theory, gran canonica monte caro, and moecular dynamics","authors":"Jinzhang Jia , Chaoyang Li , Peng Jia , Fengxiao Wang","doi":"10.1016/j.comptc.2025.115622","DOIUrl":"10.1016/j.comptc.2025.115622","url":null,"abstract":"<div><div>To elucidate the wetting mechanisms of different functional groups at the molecular scale, this study systematically investigated the interaction mechanisms between 11 functional groups in coal and water using Density Functional Theory (DFT), Gran Canonica Monte Caro (GCMC), and Moecular Dynamics (MD) simulation methods. The study reveals that functional group polarity can be quantitatively distinguished by electrostatic potential maxima. As the sole bipolar functional group, the carboxyl group exhibits both strong donor and acceptor characteristics. It forms the strongest adsorption through C=O…H and O-H…O double hydrogen bonds, demonstrating superhydrophilicity. Front-line orbital analysis revealed that hydrophilic functional groups possess lower LUMO energy levels and higher electrophilic power, facilitating electron acceptance from water molecules. RDF analysis indicated that hydrophilic functional groups exhibit lower surface water molecule aggregation, promoting spreading. This study employs multiscale simulations to elucidate the mechanism by which functional groups influence coal wettability, providing precise theoretical foundations and design guidance for optimizing coal processing through surface functional group design.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115622"},"PeriodicalIF":3.0,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691223","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 : 2025-12-03DOI: 10.1016/j.comptc.2025.115624
S.V. Thoshiba , L. Sandhiya , K. Senthilkumar
Chlorothalonil (CTN) is an organochlorine fungicide, widely used in agriculture and in protective coatings. CTN is categorized as a probable human carcinogen. In this work, reaction of CTN with atmospheric oxidants (•OH, •NO3 and O3) are studied using electronic structure calculations. Energy barrier for the reaction of CTN with •OH and •NO3 lies in the range of 7–10 kcal/mol, while for O3 initiated reactions the energy barrier is around 20 kcal/mol. At 298 K, the rate constant for the formation of CTN-OH and CTN-NO3 adduct intermediates is 3.65 × 10−13 and 3.29 × 10−18 cm3molecule−1s−1, respectively. The •OH-initiated reactions are investigated in gas and aqueous phases. The subsequent reactions of CTN-OH adduct intermediates are studied in detail to identify the possible degradation products of CTN. Results from excited state calculations show that photolysis of CTN is unlikely. The results from toxicity assessment show that the CTN and its degradation products are harmful to aquatic organisms.
{"title":"Mechanism and kinetics of chlorothalonil reaction with atmospheric oxidants","authors":"S.V. Thoshiba , L. Sandhiya , K. Senthilkumar","doi":"10.1016/j.comptc.2025.115624","DOIUrl":"10.1016/j.comptc.2025.115624","url":null,"abstract":"<div><div>Chlorothalonil (CTN) is an organochlorine fungicide, widely used in agriculture and in protective coatings. CTN is categorized as a probable human carcinogen. In this work, reaction of CTN with atmospheric oxidants (•OH, •NO<sub>3</sub> and O<sub>3</sub>) are studied using electronic structure calculations. Energy barrier for the reaction of CTN with •OH and •NO<sub>3</sub> lies in the range of 7–10 kcal/mol, while for O<sub>3</sub> initiated reactions the energy barrier is around 20 kcal/mol. At 298 K, the rate constant for the formation of CTN-OH and CTN-NO<sub>3</sub> adduct intermediates is 3.65 × 10<sup>−13</sup> and 3.29 × 10<sup>−18</sup> cm<sup>3</sup>molecule<sup>−1</sup>s<sup>−1</sup>, respectively. The •OH-initiated reactions are investigated in gas and aqueous phases. The subsequent reactions of CTN-OH adduct intermediates are studied in detail to identify the possible degradation products of CTN. Results from excited state calculations show that photolysis of CTN is unlikely. The results from toxicity assessment show that the CTN and its degradation products are harmful to aquatic organisms.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115624"},"PeriodicalIF":3.0,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145747789","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 : 2025-11-29DOI: 10.1016/j.comptc.2025.115605
Wissam Helal
The performance of two cost-efficient computational methods, the semiempirical extended tight-binding GFN2-xTB and the GFN-FF force field, was assessed for predicting the binding free energies of cucurbit[7]uril host–guest complexes with a series of cationic ammonium guests. Binding energies were computed via the supermolecular approach and decomposed into gas-phase interaction, thermostatistical, and solvation components. Both methods reproduce the general energetic trends of experimental binding affinities, with GFN-FF yielding lower mean absolute errors and standard deviations. However, the GFN2-xTB geometries are consistently closer to high-level DFT reference structures. The results indicate that while GFN-FF offers substantial computational efficiency and acceptable accuracy for screening purposes, its apparent energetic agreement may arise partly from error cancellation rather than superior physical description. The study also highlights the limitations of the single-structure supermolecular approach, particularly for flexible host–guest systems, where conformational sampling are required for a quantitatively reliable description of binding thermodynamics.
{"title":"Assessment of GFN-FF and GFN2-xTB methods for binding free energy calculations: Application to cucurbit[7]uril-cationic guest complexes","authors":"Wissam Helal","doi":"10.1016/j.comptc.2025.115605","DOIUrl":"10.1016/j.comptc.2025.115605","url":null,"abstract":"<div><div>The performance of two cost-efficient computational methods, the semiempirical extended tight-binding GFN2-xTB and the GFN-FF force field, was assessed for predicting the binding free energies of cucurbit[7]uril host–guest complexes with a series of cationic ammonium guests. Binding energies were computed via the supermolecular approach and decomposed into gas-phase interaction, thermostatistical, and solvation components. Both methods reproduce the general energetic trends of experimental binding affinities, with GFN-FF yielding lower mean absolute errors and standard deviations. However, the GFN2-xTB geometries are consistently closer to high-level DFT reference structures. The results indicate that while GFN-FF offers substantial computational efficiency and acceptable accuracy for screening purposes, its apparent energetic agreement may arise partly from error cancellation rather than superior physical description. The study also highlights the limitations of the single-structure supermolecular approach, particularly for flexible host–guest systems, where conformational sampling are required for a quantitatively reliable description of binding thermodynamics.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115605"},"PeriodicalIF":3.0,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691180","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}
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