Pub Date : 2024-11-12DOI: 10.1016/j.comptc.2024.114987
Jiankai Ou , Lufang Zhao , Yang Long , Yu Jiang , Xin Mu , Jinbao Huang , Hong Wang
In this paper, the mechanisms of catalytic pyrolysis of tetrabromobisphenol A (TBBPA) by calcium oxide (CaO) were studied through density functional theory methods. The results indicate that the phenolic hydroxyl group of TBBPA is the preferred site for CaO to extract protons, and the generated anion further transforms into 2,6-dibromophenol via demethylation and hydrogen transfer reactions. The reaction activity of CaO with hydrogen bromide is relatively high, with an energy barrier of 133.2 kJ/mol. CaO produces calcium ions, which combine with bromine ions to form calcium bromide to achieve the purpose of fixing bromine. In addition, the participation of calcium ions results in the OH bond being easier to crack, which further lowers the reaction energy barrier of keto-enol tautomerism reactions H2O produced during catalytic pyrolysis also has an obvious catalytic effect, and the energy barrier of the keto-enol tautomerism reaction decreased from 309.1 kJ/mol to 150.6 kJ/mol with the participation of H2O.
{"title":"Catalytic pyrolysis mechanism of tetrabromobisphenol A by calcium oxide: A density functional theory study","authors":"Jiankai Ou , Lufang Zhao , Yang Long , Yu Jiang , Xin Mu , Jinbao Huang , Hong Wang","doi":"10.1016/j.comptc.2024.114987","DOIUrl":"10.1016/j.comptc.2024.114987","url":null,"abstract":"<div><div>In this paper, the mechanisms of catalytic pyrolysis of tetrabromobisphenol A (TBBPA) by calcium oxide (CaO) were studied through density functional theory methods. The results indicate that the phenolic hydroxyl group of TBBPA is the preferred site for CaO to extract protons, and the generated anion further transforms into 2,6-dibromophenol via demethylation and hydrogen transfer reactions. The reaction activity of CaO with hydrogen bromide is relatively high, with an energy barrier of 133.2 kJ/mol. CaO produces calcium ions, which combine with bromine ions to form calcium bromide to achieve the purpose of fixing bromine. In addition, the participation of calcium ions results in the O<img>H bond being easier to crack, which further lowers the reaction energy barrier of keto-enol tautomerism reactions H<sub>2</sub>O produced during catalytic pyrolysis also has an obvious catalytic effect, and the energy barrier of the keto-enol tautomerism reaction decreased from 309.1 kJ/mol to 150.6 kJ/mol with the participation of H<sub>2</sub>O.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114987"},"PeriodicalIF":3.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657024","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 : 2024-11-12DOI: 10.1016/j.comptc.2024.114985
Hui Liu , Zijian Han , Yunxiang Lu , Zhijian Xu , Weiliang Zhu
Cation–anion chalcogen bonds (ChBs) have been frequently observed in the X-ray crystals of the salts formed by chalcogenated cations and a diversity of anions. In this work, we first collected a huge number of crystal structures consisting of cation–anion ChBs from the Cambridge Structural Database (CSD). Then, a set of ion-pairing complexes of chalcogenated cations with four anions (Cl−, Br−, I− and NO3−) were selected to study such interactions found in crystal structures. Owing to the much short bonding distances and the considerably large absolute binding energies, cation–anion ChBs in the complexes are very strong, leading to some degree of covalency. These interactions are directional both in solid state and in gas phase, and heavier ChBs tend to have a higher covalent content. As revealed by energy decomposition analysis, the orbital term has an important contribution to the attraction of ChBs between cations and anions.
{"title":"Cation–anion chalcogen bonds in ion pairs: A combined crystallographic survey and computational investigation","authors":"Hui Liu , Zijian Han , Yunxiang Lu , Zhijian Xu , Weiliang Zhu","doi":"10.1016/j.comptc.2024.114985","DOIUrl":"10.1016/j.comptc.2024.114985","url":null,"abstract":"<div><div>Cation–anion chalcogen bonds (ChBs) have been frequently observed in the X-ray crystals of the salts formed by chalcogenated cations and a diversity of anions. In this work, we first collected a huge number of crystal structures consisting of cation–anion ChBs from the Cambridge Structural Database (CSD). Then, a set of ion-pairing complexes of chalcogenated cations with four anions (Cl<sup>−</sup>, Br<sup>−</sup>, I<sup>−</sup> and NO<sub>3</sub><sup>−</sup>) were selected to study such interactions found in crystal structures. Owing to the much short bonding distances and the considerably large absolute binding energies, cation–anion ChBs in the complexes are very strong, leading to some degree of covalency. These interactions are directional both in solid state and in gas phase, and heavier ChBs tend to have a higher covalent content. As revealed by energy decomposition analysis, the orbital term has an important contribution to the attraction of ChBs between cations and anions.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114985"},"PeriodicalIF":3.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657036","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 : 2024-11-12DOI: 10.1016/j.comptc.2024.114988
Hoang Van Ngoc, Huynh Thi Phuong Thuy
The study investigated the adsorption of N, P, and Ne atoms on boron-germanene nanoribbons (BGeNRs) using density functional theory (DFT) and the Vienna Ab initio Simulation Package (VASP). Results indicated that both the pristine and adsorbed configurations exhibited metallic behavior. While the pristine and Ne-adsorbed configurations were nonmagnetic, the N- and P-adsorbed configurations displayed magnetic moments of 1.81 μB and 1.21 μB, respectively. The N-adsorbed configuration had the lowest adsorption energy, whereas the Ne-adsorbed configuration exhibited a positive adsorption energy. Multi-orbital hybridization analysis revealed that hybridization processes predominantly occurred in the conduction band at energy levels corresponding to the σ bond. Charge density difference analysis showed significant charge transfer between the substrate and the adsorbed elements. Additionally, optical properties, including the real and imaginary parts of the dielectric function, absorption coefficient, and electron-hole density, were systematically examined to highlight the variations. The findings underscore the potential application of BGeNR materials in nanosensors.
该研究利用密度泛函理论（DFT）和维也纳 Ab initio 仿真软件包（VASP）研究了 N、P 和 Ne 原子在硼-锗纳米带（BGeNRs）上的吸附。结果表明，原始构型和吸附构型都表现出金属特性。原始构型和Ne吸附构型没有磁性，而N和P吸附构型的磁矩分别为1.81 μB和1.21 μB。N 吸附构型的吸附能最低，而 Ne 吸附构型的吸附能为正值。多轨道杂化分析表明，杂化过程主要发生在导带中与σ键对应的能级上。电荷密度差分析表明，基底和吸附元素之间存在明显的电荷转移。此外，还系统地研究了光学特性，包括介电常数的实部和虚部、吸收系数和电子-空穴密度，以突出这些变化。这些发现强调了 BGeNR 材料在纳米传感器中的潜在应用。
{"title":"Research on N, Ne, and P adsorption on boron-germanene nanoribbons for nano sensor applications","authors":"Hoang Van Ngoc, Huynh Thi Phuong Thuy","doi":"10.1016/j.comptc.2024.114988","DOIUrl":"10.1016/j.comptc.2024.114988","url":null,"abstract":"<div><div>The study investigated the adsorption of N, P, and Ne atoms on boron-germanene nanoribbons (BGeNRs) using density functional theory (DFT) and the Vienna Ab initio Simulation Package (VASP). Results indicated that both the pristine and adsorbed configurations exhibited metallic behavior. While the pristine and Ne-adsorbed configurations were nonmagnetic, the N- and P-adsorbed configurations displayed magnetic moments of 1.81 μ<sub>B</sub> and 1.21 μ<sub>B</sub>, respectively. The <em>N</em>-adsorbed configuration had the lowest adsorption energy, whereas the Ne-adsorbed configuration exhibited a positive adsorption energy. Multi-orbital hybridization analysis revealed that hybridization processes predominantly occurred in the conduction band at energy levels corresponding to the σ bond. Charge density difference analysis showed significant charge transfer between the substrate and the adsorbed elements. Additionally, optical properties, including the real and imaginary parts of the dielectric function, absorption coefficient, and electron-hole density, were systematically examined to highlight the variations. The findings underscore the potential application of BGeNR materials in nanosensors.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114988"},"PeriodicalIF":3.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657518","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 : 2024-11-12DOI: 10.1016/j.comptc.2024.114986
Qiman Liu , Manli Zhang
The Ag-Sn alloys are famous ancient intermetallics, with the Ag3Sn being a crucial component of the phase diagram. Recently, Ag3Sn nanoparticles showcase efficient catalytic CO oxidation capabilities. Here, structural features and stability of (Ag3Sn)n (n = 1–6) clusters are first analyzed in detail. The results reveal that structures of them evolve from cages to close-packed icosahedra, where Ag are distributed on cores and gradually aggregated, whereas Sn occupy edge positions and become dispersed. Moreover, the icosahedral (Ag3Sn)3 has a higher stability than that of its neighbors and can maintain the structural integrity at 700 K. The molecular orbitals reveal that the (Ag3Sn)3 has an electronic open-shell configuration of 1S21P61D102S21F1, which is confirmed by the density of states. Electrostatic potential surfaces show that (Ag3Sn)n have significant electron-deficient σ-hole regions at Ag sites, which can make CO stretching frequencies and bond lengths have red-shifts. Adsorption energies between (Ag3Sn)n and CO display odd–even oscillations, ranging from (0.43–0.68) eV, and the direction of charge flows is from CO → clusters. Our work provides inferences to structure evolutions and adsorptions of the Ag3Sn alloy at the atomic level.
{"title":"Geometrical features and chemical adsorptions of (Ag3Sn)n clusters","authors":"Qiman Liu , Manli Zhang","doi":"10.1016/j.comptc.2024.114986","DOIUrl":"10.1016/j.comptc.2024.114986","url":null,"abstract":"<div><div>The Ag-Sn alloys are famous ancient intermetallics, with the Ag<sub>3</sub>Sn being a crucial component of the phase diagram. Recently, Ag<sub>3</sub>Sn nanoparticles showcase efficient catalytic CO oxidation capabilities. Here, structural features and stability of (Ag<sub>3</sub>Sn)<sub>n</sub> (n = 1–6) clusters are first analyzed in detail. The results reveal that structures of them evolve from cages to close-packed icosahedra, where Ag are distributed on cores and gradually aggregated, whereas Sn occupy edge positions and become dispersed. Moreover, the icosahedral (Ag<sub>3</sub>Sn)<sub>3</sub> has a higher stability than that of its neighbors and can maintain the structural integrity at 700 K. The molecular orbitals reveal that the (Ag<sub>3</sub>Sn)<sub>3</sub> has an electronic open-shell configuration of 1S<sup>2</sup>1P<sup>6</sup>1D<sup>10</sup>2S<sup>2</sup>1F<sup>1</sup>, which is confirmed by the density of states. Electrostatic potential surfaces show that (Ag<sub>3</sub>Sn)<sub>n</sub> have significant electron-deficient σ-hole regions at Ag sites, which can make C<img>O stretching frequencies and bond lengths have red-shifts. Adsorption energies between (Ag<sub>3</sub>Sn)<sub>n</sub> and CO display odd–even oscillations, ranging from (0.43–0.68) eV, and the direction of charge flows is from CO → clusters. Our work provides inferences to structure evolutions and adsorptions of the Ag<sub>3</sub>Sn alloy at the atomic level.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114986"},"PeriodicalIF":3.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657676","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 : 2024-11-09DOI: 10.1016/j.comptc.2024.114984
Qiaoyu Wei , Hui Wang , Andrey V. Zibarev
Chalcogen bonding (ChB) is an σ-hole-driven secondary bonding interaction (SBI). The crystalline 2,1,3-benzochalcogenadiazoles involved in organic optoelectronics is exemplified by [E···N]2 supramolecular synthon. For 5,6- R2 −2,1,3-pyrazinochalcogenadiazoles E-M and [E···N]2-bonded (E-M)2 (E = S, Se, Te; R/M = H/1, Me/2, CN/3), gas-phase and dichloromethane solution calculations are performed. The molecular electrostatic potential suggests that changes in E, R influence σ- and π-holes of E-M/(E-M)2. Distant R acts via long-range electrostatic field effect. ChB strength increases in the order S < Se < Te, and (E-2)2 < (E-1)2 < (E-3)2. The main driving forces are electrostatic and dispersion interactions. Crystalline S-1 and Se-2 have head-to-head dimers. Se-3 shows head-to-tail chains via Se···NcyanoChB. A competition between different ChB, and, between ChB and other SBIs, should be considered in the design and synthesis of new E-M/(E-M)2 for fundamentals and applications.
{"title":"Influence of 2,1,3-pyrazinochalcogenadiazoles structure on their dimerization via chalcogen bonding (chalcogen = S, Se, Te)","authors":"Qiaoyu Wei , Hui Wang , Andrey V. Zibarev","doi":"10.1016/j.comptc.2024.114984","DOIUrl":"10.1016/j.comptc.2024.114984","url":null,"abstract":"<div><div>Chalcogen bonding (<em>ChB</em>) is an σ-hole-driven secondary bonding interaction (SBI). The crystalline 2,1,3-<em>benzo</em>chalcogenadiazoles involved in organic optoelectronics is exemplified by [E···N]<sub>2</sub> supramolecular synthon. For 5,6- R<sub>2</sub> −2,1,3-<em>pyrazino</em>chalcogenadiazoles E-<strong>M</strong> and [E···N]<sub>2</sub>-bonded (E-<strong>M</strong>)<sub>2</sub> (E = S, Se, Te; R/<strong>M</strong> = H/<strong>1</strong>, Me/<strong>2</strong>, CN/<strong>3</strong>), gas-phase and dichloromethane solution calculations are performed. The molecular electrostatic potential suggests that changes in E, R influence σ- and π-holes of E-<strong>M</strong>/(E-<strong>M</strong>)<sub>2</sub>. Distant R acts via long-range electrostatic field effect. <em>ChB</em> strength increases in the order S < Se < Te, and (E-<strong>2</strong>)<sub>2</sub> < (E-<strong>1</strong>)<sub>2</sub> < (E-<strong>3</strong>)<sub>2</sub>. The main driving forces are electrostatic and dispersion interactions. Crystalline S-<strong>1</strong> and Se-<strong>2</strong> have head-to-head dimers. Se-<strong>3</strong> shows head-to-tail chains via Se···N<sub>cyano</sub> <em>ChB</em>. A competition between different <em>ChB</em>, and, between <em>ChB</em> and other SBIs, should be considered in the design and synthesis of new E-<strong>M</strong>/(E-<strong>M</strong>)<sub>2</sub> for fundamentals and applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114984"},"PeriodicalIF":3.0,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657677","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 : 2024-11-09DOI: 10.1016/j.comptc.2024.114942
Hanna D. Hobbs, Lowen M. Hobbs, Robert W. Zoellner
Density functional theory calculations, at the ωB97X-D/6-311+G* level of theory, were performed on homoleptic fluoro-copper complexes [CuFn]x, n = 1 through 6 and x = 3+ through 5−, to determine the highest positive and lowest negative copper oxidation states that can be supported in these complexes. Only singlet and doublet spin states were investigated. All fluoro-copper stoichiometries stabilized copper(III) or greater. However, some stoichiometries stabilized oxidation states up to copper(VI), and the greatest positive copper oxidation state was copper(VIII) in the distorted octahedral [CuF6]2+ cation. Oxidation states as negative as copper(–IV) in the diatomic [CuF]5− anion and copper(–III) in the triatomic [CuF2]5− were also observed as optimized minima, although no negative oxidation states were calculated to exist for fluoro-copper complexes containing more than two fluorine atoms. No singlet or doublet fluoro-copper complexes with charges more positive than 3+, more negative than 5−, or of Cu(VII), could be optimized.
{"title":"The limits of copper oxidation states from density functional theory computations: Fluoro-copper complexes, [CuFn]x, where n = 1 through 6 and x = 3+ through 5−","authors":"Hanna D. Hobbs, Lowen M. Hobbs, Robert W. Zoellner","doi":"10.1016/j.comptc.2024.114942","DOIUrl":"10.1016/j.comptc.2024.114942","url":null,"abstract":"<div><div>Density functional theory calculations, at the ωB97X-D/6-311+G* level of theory, were performed on homoleptic fluoro-copper complexes [CuF<em><sub>n</sub></em>]<em><sup>x</sup></em>, <em>n</em> = 1 through 6 and <em>x</em> = 3+ through 5−, to determine the highest positive and lowest negative copper oxidation states that can be supported in these complexes. Only singlet and doublet spin states were investigated. All fluoro-copper stoichiometries stabilized copper(III) or greater. However, some stoichiometries stabilized oxidation states up to copper(VI), and the greatest positive copper oxidation state was copper(VIII) in the distorted octahedral [CuF<sub>6</sub>]<sup>2+</sup> cation. Oxidation states as negative as copper(–IV) in the diatomic [CuF]<sup>5−</sup> anion and copper(–III) in the triatomic [CuF<sub>2</sub>]<sup>5−</sup> were also observed as optimized minima, although no negative oxidation states were calculated to exist for fluoro-copper complexes containing more than two fluorine atoms. No singlet or doublet fluoro-copper complexes with charges more positive than 3+, more negative than 5−, or of Cu(VII), could be optimized.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114942"},"PeriodicalIF":3.0,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657038","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}
Here, we studied the stability, electronic characteristics, and HER catalytic performance of transition metal single atom catalysts, both with and without the presence of chlorine ligand. The findings indicate that all catalysts, except for Au, Au-Cl, Ag, Ag-Cl, are thermodynamically stable. We found 3d transition metals are more stable than those in the 4d and 5d series. Ag-Cl, Sc, Ag, Fe-Cl, and Cr-Cl have the poorest electrochemical stability. We found a negative Pearson correlation between Fermi energy and formation energy for TM-Cl, which is opposite to the trend observed for bare TM catalysts. The higher HER activity of chlorine bonded system for the early 3d TM suggests that the downshifting of the d-band center facilitates the activity. We also observed a periodic trend in the d-band center for both TM and TM-Cl systems. Mn-Cl, Cr-Cl, Ti-Cl, Fe-Cl, V-Cl and Zn emerged as the superior catalysts in our study series.
在此，我们研究了过渡金属单原子催化剂的稳定性、电子特性和 HER 催化性能，包括氯配体存在和不存在的情况。研究结果表明，除 Au、Au-Cl、Ag、Ag-Cl 外，所有催化剂都具有热力学稳定性。我们发现 3d 过渡金属比 4d 和 5d 系列的金属更稳定。Ag-Cl、Sc、Ag、Fe-Cl 和 Cr-Cl 的电化学稳定性最差。我们发现 TM-Cl 的费米能与形成能之间存在负的皮尔逊相关性，这与裸 TM 催化剂的趋势相反。早期 3d TM 的氯键体系具有更高的 HER 活性，这表明 d 带中心的下移促进了活性的提高。我们还观察到 TM 和 TM-Cl 体系的 d 波段中心呈周期性变化趋势。在我们的研究系列中，Mn-Cl、Cr-Cl、Ti-Cl、Fe-Cl、V-Cl 和 Zn 成为最优秀的催化剂。
{"title":"Computational screening and investigation of ligand effect on TM single atom catalyst for hydrogen evolution reaction","authors":"N.J. Hemavathi , Chiranjib Majumder , Suman Kalyan Sahoo","doi":"10.1016/j.comptc.2024.114981","DOIUrl":"10.1016/j.comptc.2024.114981","url":null,"abstract":"<div><div>Here, we studied the stability, electronic characteristics, and HER catalytic performance of transition metal single atom catalysts, both with and without the presence of chlorine ligand. The findings indicate that all catalysts, except for Au, Au-Cl, Ag, Ag-Cl, are thermodynamically stable. We found 3d transition metals are more stable than those in the 4d and 5d series. Ag-Cl, Sc, Ag, Fe-Cl, and Cr-Cl have the poorest electrochemical stability. We found a negative Pearson correlation between Fermi energy and formation energy for TM-Cl, which is opposite to the trend observed for bare TM catalysts. The higher HER activity of chlorine bonded system for the early 3d TM suggests that the downshifting of the d-band center facilitates the activity. We also observed a periodic trend in the d-band center for both TM and TM-Cl systems. Mn-Cl, Cr-Cl, Ti-Cl, Fe-Cl, V-Cl and Zn emerged as the superior catalysts in our study series.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114981"},"PeriodicalIF":3.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657037","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 : 2024-11-08DOI: 10.1016/j.comptc.2024.114951
Yue-hong Yin, Chao Lu
Non-covalent interactions play an important role in numerous fields, particularly in physical hydrogen storage. The hydrogen storage properties of C3N are investigated by DFT calculations. The results indicated that H2 and C3N form physical adsorption. The electronic structure analysis demonstrates that both the covalent and electrostatic interactions between H2 and C3N are rather weak, while IRI analysis reveals that their interactions belong to non-valent interactions, and the further energy decomposition based on SAPT suggests that the sources of interaction energies differ for the two configurations TCR and TNR. For TCR, the induction energy is the primary contributor, for TNR, the electrostatic interaction dominates. Our comprehensive study not only enhances our understanding of the intricate interactions between H2 and C3N but also serves as a valuable guide for enhancing the adsorption strength in physical hydrogen storage systems.
{"title":"The non-covalent interaction between C3N and H2","authors":"Yue-hong Yin, Chao Lu","doi":"10.1016/j.comptc.2024.114951","DOIUrl":"10.1016/j.comptc.2024.114951","url":null,"abstract":"<div><div>Non-covalent interactions play an important role in numerous fields, particularly in physical hydrogen storage. The hydrogen storage properties of C<sub>3</sub>N are investigated by DFT calculations. The results indicated that H<sub>2</sub> and C<sub>3</sub>N form physical adsorption. The electronic structure analysis demonstrates that both the covalent and electrostatic interactions between H<sub>2</sub> and C<sub>3</sub>N are rather weak, while IRI analysis reveals that their interactions belong to non-valent interactions, and the further energy decomposition based on SAPT suggests that the sources of interaction energies differ for the two configurations T<sub><span>CR</span></sub> and T<sub><span>NR</span></sub>. For T<sub><span>CR</span></sub>, the induction energy is the primary contributor, for T<sub><span>NR</span></sub>, the electrostatic interaction dominates. Our comprehensive study not only enhances our understanding of the intricate interactions between H<sub>2</sub> and C<sub>3</sub>N but also serves as a valuable guide for enhancing the adsorption strength in physical hydrogen storage systems.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114951"},"PeriodicalIF":3.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657674","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}
Singlet fission (SF) suffers from the scarcity of available SF chromophores and sensitizers. Tetracene, pentacene and their derivatives, are two typical model systems for the study of SF photophysical phenomena. Herein, the analogues of polyacenes, furanoacenes and their derivatives, were evaluated as potential SF chromophores and sensitizers through a theoretical study. The primary photostability were evaluated by the frontier molecular orbital energy levels, diradical characters and SF relevant excited state energies according to the type-I and −II photodegradation mechanisms. The cross-substitutions by combining central substitutions with triple bonds and terminal substituents enhance photostability, tune the SF relevant excited states efficiently, and give more appropriate E(T1) to be SF sensitizers. This work helps to give better understanding of the electronic structures and SF capability of furanoacenes.
单裂变（SF）的问题在于可用的 SF 发色团和敏化剂稀缺。四碳烯、五碳烯及其衍生物是研究 SF 光物理现象的两个典型模型系统。在此，我们通过理论研究评估了作为潜在 SF 发色团和敏化剂的聚碳酸酯类似物、呋喃烯及其衍生物。根据 I 型和 II 型光降解机制，通过前沿分子轨道能级、二极性特征和 SF 相关激发态能量评估了主要光稳定性。通过将中心取代与三键和末端取代基相结合的交叉取代，提高了光稳定性，有效地调节了与 SF 有关的激发态，并给出了更合适的 E（T1），从而成为 SF 增敏剂。这项工作有助于更好地理解呋喃并烯类化合物的电子结构和 SF 能力。
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Pub Date : 2024-11-07DOI: 10.1016/j.comptc.2024.114936
Fazal Dayan, Adnan Shahzad, Imad Ud Din
Identifying new electrode materials for K-ion batteries (KIBs) is still difficult since battery technology lacks an effective high-throughput screening approach. The durability, affordability, safety, and resemblance to Li-ion batteries of KIBs have garnered them tremendous attention. Porphyrin-based materials have become attractive options because of their generous surface area and advantageous photo-physical characteristics. As effective cathodic materials for KIBs, porphyrin Schiff base nanostructures (SBNs) are suggested in this work. Our goal was to improve Potassium-ion doped porphyrin derivatives by using Density Functional Theory (DFT) with the Gaussian 09 program with a B3LYP/6-31G(d) basis set. We also calculated important electronic parameters such as the band gap, electrophilicity, chemical potential, and frontier orbitals (HOMO and LUMO). The determined HOMO-LUMO gaps for compounds 1 to 4 were 2.97, 1.52, 1.38, and 1.36 respectively. The computed gaps indicate that the reactivity of the compounds increases from 1 to 4, whereas the stability decreases from 1 to 4.
Based on these computational observations, it is expected that this theoretical analysis will provide a basis for future researchers to explore the practical applications of these compounds through experimentation.
{"title":"Designing and investigating electronic states of porphyrin Schiff bases nanoflakes, cathode materials for K+ - batteries","authors":"Fazal Dayan, Adnan Shahzad, Imad Ud Din","doi":"10.1016/j.comptc.2024.114936","DOIUrl":"10.1016/j.comptc.2024.114936","url":null,"abstract":"<div><div>Identifying new electrode materials for K-ion batteries (KIBs) is still difficult since battery technology lacks an effective high-throughput screening approach. The durability, affordability, safety, and resemblance to Li-ion batteries of KIBs have garnered them tremendous attention. Porphyrin-based materials have become attractive options because of their generous surface area and advantageous photo-physical characteristics. As effective cathodic materials for KIBs, porphyrin Schiff base nanostructures (SBNs) are suggested in this work. Our goal was to improve Potassium-ion doped porphyrin derivatives by using Density Functional Theory (DFT) with the Gaussian 09 program with a B3LYP/6-31G(d) basis set. We also calculated important electronic parameters such as the band gap, electrophilicity, chemical potential, and frontier orbitals (HOMO and LUMO). The determined HOMO-LUMO gaps for compounds <strong>1</strong> to <strong>4</strong> were 2.97, 1.52, 1.38, and 1.36 respectively. The computed gaps indicate that the reactivity of the compounds increases from <strong>1</strong> to <strong>4</strong>, whereas the stability decreases from <strong>1</strong> to <strong>4</strong>.</div><div>Based on these computational observations, it is expected that this theoretical analysis will provide a basis for future researchers to explore the practical applications of these compounds through experimentation.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114936"},"PeriodicalIF":3.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657675","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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