Computational and Theoretical Chemistry最新文献

{"title":"Adsorption of organic pollutants on B12N12 and Al12N12 nanocages","authors":"Remya Geetha Sadasivan Nair,&nbsp;Arun Kumar Narayanan Nair,&nbsp;Shuyu Sun,&nbsp;Bicheng Yan","doi":"10.1016/j.comptc.2025.115187","DOIUrl":"10.1016/j.comptc.2025.115187","url":null,"abstract":"<div><div>The adsorption of twenty-four aromatic pollutants (1,3-dichlorobenzene, benzene, ethyl benzene, 1,4-dinitrobenzene, 4-fluorophenol, phenyl acetate, etc.) onto B₁₂N₁₂ and Al₁₂N₁₂ nanocages is studied using density functional theory. The pollutant molecules are typically bound to the B/Al atoms of the B₁₂N₁₂ and Al₁₂N₁₂ nanocages. Benzene and chlorine−/alkyl-substituted benzenes are observed to be weakly adsorbed on the B₁₂N₁₂ and Al₁₂N₁₂ nanocages. All other pollutant molecules are strongly adsorbed on the B₁₂N₁₂ and Al₁₂N₁₂ nanocages. Importantly, the adsorption energies are linearly proportional to the MESP minimum values of the pollutant molecules. A striking change in the reactivity parameter (e.g. global electrophilicity) of the B₁₂N₁₂ and Al₁₂N₁₂ nanocages is usually found for the adsorption of nitro-substituted aromatic compounds and carbonyl-containing compounds. The QTAIM analyses point to a noncovalent character for the interaction of benzene and chlorine−/alkyl-substituted benzenes with the B₁₂N₁₂ nanocage, and to a partial covalent character for the interaction of the other studied pollutant molecules with the B₁₂N₁₂ nanocage. However, an opposite trend is observed for the pollutant/Al₁₂N₁₂ system. Our results show a relatively high stability of the complexes of nitro-/OH−/carbonyl-containing compounds with B₁₂N₁₂ and Al₁₂N₁₂ in water.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115187"},"PeriodicalIF":3.0,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143636836","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Topological analysis of metal–organic frameworks: A regression approach to enhance molecular modeling","authors":"Divya A. ,&nbsp;Karunyan A.","doi":"10.1016/j.comptc.2025.115156","DOIUrl":"10.1016/j.comptc.2025.115156","url":null,"abstract":"<div><div>The novel metal–organic framework crystallized in a parsimonious mep topology based on Frank-Kasper polyhedra, showcasing the potential for innovative structural designs in MOF chemistry. This work aims to investigate the metal–organic framework with this feature through topological analysis. The primary objective of this research paper is to conduct an in-depth analysis of the correlation between topological descriptors and the total <span><math><mi>π</mi></math></span>-electron energy exhibited by a diverse range of metal–organic frameworks. Through a meticulous examination of various MOFs, the paper endeavors to construct a comprehensive regression model that can effectively elucidate the intricate structural attributes and potential functionalities associated with these unique materials. Furthermore, the study aims to offer valuable insights into the interconnectivity and spatial arrangement of atoms within MOF frameworks, thereby enhancing our comprehension of their chemical, physical, and biological characteristics. Moreover, the research delves into the feasibility of using regression models as predictive tools for numerous molecular properties, presenting a cost-effective alternative to traditional experimental and computational methodologies. By exploring these avenues, the paper contributes to the ongoing discourse on the utilization of mathematical models in the realm of material science and opens up new possibilities for enhancing our understanding of MOFs and their diverse applications in various fields. In conclusion, this study sheds light on the potential implications of leveraging regression analysis in the realm of MOF research, paving the way for innovative approaches to studying and harnessing the unique properties of these intriguing materials.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115156"},"PeriodicalIF":3.0,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Adsorption of Linuron by the chitosan-bentonite composite: Kinetic, thermodynamic, and theoretical studies","authors":"Lama Rissouli ,&nbsp;Mohamed Berradi ,&nbsp;Mohamed Chabbi ,&nbsp;Abdesselam Eddaoukhi ,&nbsp;Ikram Chaer ,&nbsp;Naoual El-Aouni ,&nbsp;Omar Berradi ,&nbsp;Ahmed El Yacoubi ,&nbsp;Safi Zaki ,&nbsp;Avni Berisha ,&nbsp;Abderrahim El Bachiri ,&nbsp;Nuha Wazzan ,&nbsp;Mohamed Benicha","doi":"10.1016/j.comptc.2025.115160","DOIUrl":"10.1016/j.comptc.2025.115160","url":null,"abstract":"<div><div>There is an increasing need for research on the use of cost-effective materials to decontaminate wastewater polluted with Linuron. In this context, we investigated the application of a chitosan-bentonite composite for the removal of Linuron from aqueous solutions. The experiments were conducted in batch mode under varying experimental conditions. Adsorption was examined as a function of mass ratio, adsorbent amount, initial herbicide concentration, contact time, and pH. The Langmuir and Freundlich models were applied to analyze the results, while the kinetics were described using the pseudo-first and pseudo-second-order models. The results indicated that the Langmuir model provided a better fit for Linuron adsorption, whereas the pseudo-first-order model more accurately described the kinetics at the optimum pH. On the other hand, the molecular geometry of Linuron in aqueous solutions was determined using the Density Functional Theory (DFT) method at the B3LYP/6-311+g(d,p) level of theory, along with the Conductor-like Polarizable Continuum Model (CPCM) solvation model. The global chemical reactivity indicators were calculated based on the frontier molecular orbitals. Local reactivity indices were determined using Mulliken charges, natural population charges, and Fukui functions. Furthermore, the optimal adsorption configuration of Linuron molecules was identified to accurately estimate the energy involved and ensure the success of the adsorption process. To analyze and calculate adsorption energies, a model was developed to represent the interaction between the adsorbed molecule and the clay surface. The Monte Carlo (MC) method was used to thoroughly examine the configuration. The presence of strong interactions and negative adsorption energies indicates that Linuron molecules are attracted to and stable at the interface. Molecular dynamics (MD) simulations further validated the robustness of the results.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115160"},"PeriodicalIF":3.0,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143636835","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic insights into the interaction of NO, char‑nitrogen and NH3 during ammonia-coal combustion","authors":"Zhi Zheng ,&nbsp;Jun Shen ,&nbsp;Zhenqing Han ,&nbsp;Yu Chen ,&nbsp;Sha Wang ,&nbsp;Yifan Bai","doi":"10.1016/j.comptc.2025.115183","DOIUrl":"10.1016/j.comptc.2025.115183","url":null,"abstract":"<div><div>Ammonia-coal co-combustion effectively reduces carbon dioxide and nitrogen oxide emissions. In this process, nitrogen in char is converted to N₂ in the NH₃ atmosphere. Using density functional theory, the researchers have explored the role of oxygen, which not only increases the energy barrier of the final product, but also facilitates the rapid conversion of char nitrogen to N₂. In the NH₃/O₂ environment, hydroxyl groups play a crucial role in the formation of water molecules. In addition, according to the theoretical calculation and experimental results, it is found that the desorption rate of CO is slightly higher than that of NO.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115183"},"PeriodicalIF":3.0,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143609349","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DFT approach study of the hydrogenation of Ni- and V- octaethylporphyrins catalyzed by MoS2 promoted with Fe, Co or Ni","authors":"Miriam Ballesteros-Olvera ,&nbsp;Carolina Zuriaga-Monroy ,&nbsp;Raúl Oviedo-Roa ,&nbsp;Estela Mayoral-Villa ,&nbsp;Laura Michelle Jiménez-Díaz ,&nbsp;Jaime Klapp ,&nbsp;Irineo-Pedro Zaragoza ,&nbsp;José-Manuel Martínez-Magadán","doi":"10.1016/j.comptc.2025.115173","DOIUrl":"10.1016/j.comptc.2025.115173","url":null,"abstract":"<div><div>The effect of promoting the catalytic surface of MoS₂ with Fe, Co and Ni, utilized in the hydrodemetallization reactions of heavy oil fractions, was investigated using the model porphyrins VO-octaethylporphyrinate and Ni-octaethylporphyrinate. Density Functional Theory was employed to simulate a representative chemical environment with two hydrogen molecules. For this purpose, a catalytically active site was defined. The results indicated that porphyrins exhibited the strongest chemisorption in the molybdenum-exposed region, followed by the sulfur-exposed region. Furthermore, the initial hydrogenation was favored on the Co- and Fe-promoted catalytic surfaces with both porphyrins. Similarly, the Co- and Fe-promoted surfaces interacting with Ni-OEP demonstrated strong chemisorption of a second H₂ molecule, whereas for VO-OEP, the second H₂ molecule exhibited favorable chemisorption with the Fe-promoted catalytic surface. These findings suggest that two H₂ molecules are necessary to weaken the macrocyclic bonds of the porphyrins.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115173"},"PeriodicalIF":3.0,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143628145","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical investigation on the alcoholysis reaction mechanism of nerve agents: The reaction of tabun with methanol","authors":"Rong Chen,&nbsp;Yuting Wei,&nbsp;Xiaoling Luo,&nbsp;Guoming Liang","doi":"10.1016/j.comptc.2025.115159","DOIUrl":"10.1016/j.comptc.2025.115159","url":null,"abstract":"<div><div>The alcoholysis mechanism for tabun has been systematically studied by using B3LYP/6–311++G(d,p), M06-2×/6–311++G(d,p) and MP2/6–311++G(d,p) levels. Three plausible reaction processes, the P–CN, P–N(CH₃)₂ and P–OEt disintegration pathways involving the concerted and stepwise channels are theoretically examined. To explore the effect of additional methanol and water, methanol-catalyzed and water-catalyzed alcoholysis are extensively assessed. Additionally, we also consider the effect of solvent in water by performing CPCM model at M06-2×/6–311++G(d,p) level. The results of our predictions show convincingly that the stepwise mechanism with obviously lower energy is more prominent than the concerted one and the most preferred mechanism seems to be the stepwise pathway of the P–CN cleavage channel. Moreover, our theoretical results clearly demonstrate the methanol-assisted and water-assisted alcoholysis are more easier to occur than the direct alcoholysis. Solvent effect does not have remarkable effect on the reaction mechanism. Our results certainly provide valuable information for the degradation of nerve agents.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115159"},"PeriodicalIF":3.0,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600997","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular design and theoretical investigation on novel (D)2-π-a photosensitizers based on coumarin dye: Impact of boron dipyrromethene bridge on UV–vis and optoelectronic properties","authors":"Farikou Tije ,&nbsp;Crevain Souop Tala Foadin ,&nbsp;Fridolin Tchangnwa Nya ,&nbsp;Alhadji Malloum ,&nbsp;Geh Wilson Ejuh ,&nbsp;Jeanet Conradie","doi":"10.1016/j.comptc.2025.115182","DOIUrl":"10.1016/j.comptc.2025.115182","url":null,"abstract":"<div><div>In this study, eight new photosensitizers based on the (D)₂-π-A molecular architecture were theoretically designed using two, 7-diethylaminocoumarin dyes as the donor and cyanoacrylic acid or (Z)-2-Cyano-3-phenylacrylic acid as the acceptor unit. Boron dipyrromethene (BODIPY) functionalized with various heterocycles was used as an π-bridge. We aim to enhance the light-harvesting efficiency of dyes derived from the coumarin molecule in the red and near-infrared regions of the solar spectrum. Theoretically, investigation using density functional theory (DFT) and time-dependent DFT (TD-DFT) show that all the dyes designed exhibit intense and broad absorption in the visible and near-infrared range, denoting panchromatic absorption. The maximum absorption wavelength values for all designed dyes found in acetonitrile (648 to 757 nm) with maximum molar extinction coefficients between 76,815 to 106,445 M⁻¹.cm⁻¹ are remarkably higher than those obtained for other dyes based on a single coumarin donor reported in the literature.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115182"},"PeriodicalIF":3.0,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619228","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pentavalent pnictogen bonds involving triarylpnictogen catecholates as strong Lewis acids: Crystallographic survey and theoretical analysis","authors":"Ruotong Liu ,&nbsp;Zijian Han ,&nbsp;Yunxiang Lu ,&nbsp;Zhijian Xu ,&nbsp;Weiliang Zhu","doi":"10.1016/j.comptc.2025.115171","DOIUrl":"10.1016/j.comptc.2025.115171","url":null,"abstract":"<div><div>As a novel class of Lewis acids, triarylpnictogen(V) catecholate compounds have attracted increasing attention in anion binding and transport, supramolecular chemistry, and organocatalysis. In this work, pentavalent pnictogen bonds (PnBs) formed by these compounds and chloride ion were investigated in detail via the combination of crystallographic data analysis and quantum chemical calculations. Owing to the much shorter intermolecular distances and the considerably more negative binding energies, pentavalent PnBs show a remarkably enhanced strength compared with conventional trivalent PnBs, leading to a greater degree of covalency for hypervalent PnBs. Energy decomposition analysis revealed that both the electrostatic and the orbital terms contribute significantly to the attraction of pentavalent PnBs, while the Pauli repulsion term plays an important role in rationalizing the observed Lewis acidic tendency of pnictogens. In addition, the influence of different substituents either in the phenyl rings or in the catecholate group was also examined for these interactions.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115171"},"PeriodicalIF":3.0,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600998","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DFT calculations on single lanthanide atoms: Is the task as simple as it seems?","authors":"Vladimir A. Basiuk","doi":"10.1016/j.comptc.2025.115170","DOIUrl":"10.1016/j.comptc.2025.115170","url":null,"abstract":"<div><div>We tested three spin-unconstrained DFT calculation schemes (PBE-D2/DNP theoretical level with DSPP and ECP pseudopotentials within DMol³ module, and PBE-D2/def2-ECP within TURBOMOLE package) to verify which of them allows for the successful single-point calculations on the full series of isolated lanthanide atoms (La to Lu), and compared the basic electronic characteristics obtained such as spin values (that is, the number of unpaired electrons), spin density plots, HOMO-LUMO plots, and the gap energies. A number of serious problems were found with TURBOMOLE (impossibility of calculations for Tm and Lu; unrealistic spin values for La, Eu and Tb), but a fractional orbital occupancy was never detected at the target thermal smearing value of 0.0001 Ha. When employing DMol³, the full set can be completed with DSPP; with ECP, with the exception of Tb. However, in some cases a fractional orbital occupancy was detected.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115170"},"PeriodicalIF":3.0,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143591366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigations on acid/base-catalyzed hydrolysis mechanisms of mono(2-hydroxyethyl) terephthalate using quantum chemistry methods","authors":"Weifeng Xu ,&nbsp;Yang Long ,&nbsp;Song Chen ,&nbsp;Jinbao Huang ,&nbsp;Hong Wang ,&nbsp;Li Jin ,&nbsp;Jun Cheng ,&nbsp;Xinsheng Li","doi":"10.1016/j.comptc.2025.115163","DOIUrl":"10.1016/j.comptc.2025.115163","url":null,"abstract":"<div><div>The mechanisms and kinetics of acid/base-catalyzed hydrolysis of PET model compound, mono(2-hydroxyethyl) terephthalate (MHET), were evaluated by quantum chemical methods. For acid-catalyzed hydrolysis, the most feasible degradation pathways involved the protonation of the most negative potential oxygen atom O_carbonyl. The ester bond was subsequently cleaved to form terephthalic acid (TPA) and a cationic intermediate, with the energy barrier of 94.0 kJ/mol. For base-catalyzed hydrolysis, [OH]⁻ tends to attack the C_carbonyl atom of MHET to form an anionic intermediate, requiring overcoming a barrier height of 158.3 kJ/mol due to the electron outflow from the lone pair of [OH]⁻ to the empty <em>p</em> orbital of the O_carbonyl and O_ester atoms. For solvent effect, a tend was observed that related the reaction energy barrier positive correlation to the polarity of the solvent. Cations are beneficial for stabilizing the transition state, whereas counteranions did not significantly change the reaction energetics.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115163"},"PeriodicalIF":3.0,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143609350","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}