Computational and Theoretical Chemistry最新文献_第10页

Theoretical investigation on the alcoholysis reaction mechanism of nerve agents: The reaction of tabun with methanol 神经毒剂醇解反应机理的理论研究：塔苯与甲醇的反应

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-03-08 DOI: 10.1016/j.comptc.2025.115159

Rong Chen, Yuting Wei, Xiaoling Luo, Guoming Liang

{"title":"Theoretical investigation on the alcoholysis reaction mechanism of nerve agents: The reaction of tabun with methanol","authors":"Rong Chen, Yuting Wei, Xiaoling Luo, 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(CH<sub>3</sub>)<sub>2</sub> 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}

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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 基于香豆素染料的新型 (D)2-π-a 光敏剂的分子设计和理论研究：二吡咯烷硼桥对紫外-可见光和光电特性的影响

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-03-08 DOI: 10.1016/j.comptc.2025.115182

Farikou Tije , Crevain Souop Tala Foadin , Fridolin Tchangnwa Nya , Alhadji Malloum , Geh Wilson Ejuh , Jeanet Conradie

{"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 , Crevain Souop Tala Foadin , Fridolin Tchangnwa Nya , Alhadji Malloum , Geh Wilson Ejuh , 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)<sub>2</sub>-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<sup>−1</sup>.cm<sup>−1</sup> 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}

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Pentavalent pnictogen bonds involving triarylpnictogen catecholates as strong Lewis acids: Crystallographic survey and theoretical analysis 三芳基烟原儿茶酚酸盐作为强路易斯酸的五价烟原键：晶体学研究和理论分析

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-03-07 DOI: 10.1016/j.comptc.2025.115171

Ruotong Liu , Zijian Han , Yunxiang Lu , Zhijian Xu , Weiliang Zhu

{"title":"Pentavalent pnictogen bonds involving triarylpnictogen catecholates as strong Lewis acids: Crystallographic survey and theoretical analysis","authors":"Ruotong Liu , Zijian Han , Yunxiang Lu , Zhijian Xu , 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}

引用次数: 0

DFT calculations on single lanthanide atoms: Is the task as simple as it seems? 单系镧原子的DFT计算：任务像看起来那么简单吗？

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-03-07 DOI: 10.1016/j.comptc.2025.115170

Vladimir A. Basiuk

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Investigations on acid/base-catalyzed hydrolysis mechanisms of mono(2-hydroxyethyl) terephthalate using quantum chemistry methods 用量子化学方法研究酸/碱催化对苯二甲酸一（2-羟乙基）酯水解机理

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-03-06 DOI: 10.1016/j.comptc.2025.115163

Weifeng Xu , Yang Long , Song Chen , Jinbao Huang , Hong Wang , Li Jin , Jun Cheng , Xinsheng Li

{"title":"Investigations on acid/base-catalyzed hydrolysis mechanisms of mono(2-hydroxyethyl) terephthalate using quantum chemistry methods","authors":"Weifeng Xu , Yang Long , Song Chen , Jinbao Huang , Hong Wang , Li Jin , Jun Cheng , 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<sub>carbonyl</sub>. 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]<sup>−</sup> tends to attack the C<sub>carbonyl</sub> 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]<sup>−</sup> to the empty <em>p</em> orbital of the O<sub>carbonyl</sub> and O<sub>ester</sub> 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}

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Electrocatalytic potential of bare and OH-functionalized Co-N-doped pyrene for ORR and HER: A DFT study 裸和oh功能化co - n掺杂芘对ORR和HER的电催化电位：DFT研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-03-05 DOI: 10.1016/j.comptc.2025.115167

Angappan Kausalya, Thangaraj Thiruppathiraja, Senthilkumar Lakshmipathi

{"title":"Electrocatalytic potential of bare and OH-functionalized Co-N-doped pyrene for ORR and HER: A DFT study","authors":"Angappan Kausalya, Thangaraj Thiruppathiraja, Senthilkumar Lakshmipathi","doi":"10.1016/j.comptc.2025.115167","DOIUrl":"10.1016/j.comptc.2025.115167","url":null,"abstract":"<div><div>Developing efficient bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) is essential for regenerative applications such as fuel cells and water-splitting processes. Single-atom catalysts (SACs) offer advantages of low cost, high selectivity, and excellent catalytic performance in ORR and HER mechanisms. This study investigates the catalytic activity of cobalt and nitrogen-doped pyrene (Co-N-PYR) and hydroxyl-functionalized cobalt and nitrogen-doped pyrene (Co-N-PYR(OH)<sub>10</sub>) surfaces using density functional theory (DFT) calculations. The thermochemical properties reveal that ORR mechanisms on Co-N-PYR and Co-N-PYR(OH)<sub>10</sub> surfaces are highly exothermic and energetically favorable. The overall free energy changes for ORR on Co-N-PYR and Co-N-PYR(OH)<sub>10</sub> surfaces indicate spontaneous reactions. For HER, the free energy of hydrogen adsorption (ΔGH*) on Co-N-PYR(OH)<sub>10</sub> is ‐0.03 eV, close to the ideal catalyst (ΔG<sub>H</sub><sub>*</sub>≈ 0). The predicted ORR and HER overpotentials for Co-N-PYR(OH)<sub>10</sub> are 0.88 V and ‐0.03 V, respectively. These results demonstrate that Co-N-PYR(OH)<sub>10</sub> is an excellent bifunctional electrocatalyst for ORR and HER processes.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115167"},"PeriodicalIF":3.0,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143609351","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}

引用次数: 0

Aldehyde adsorption studies on α‑arsenic phosphorus monolayer – A first-principles investigation α -砷磷单分子膜上醛吸附的第一性原理研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-03-04 DOI: 10.1016/j.comptc.2025.115162

M. Vijay Balaji, V. Nagarajan, R. Chandiramouli

{"title":"Aldehyde adsorption studies on α‑arsenic phosphorus monolayer – A first-principles investigation","authors":"M. Vijay Balaji, V. Nagarajan, R. Chandiramouli","doi":"10.1016/j.comptc.2025.115162","DOIUrl":"10.1016/j.comptc.2025.115162","url":null,"abstract":"<div><div>In recent days, researchers concentrate on elemental monolayer materials owing to their superior stability, sensitivity, and selectivity towards air contaminants. Besides, one example of two-dimensional (2D) material is the α‑arsenic phosphorus monolayer (α-AsP) which resembles black phosphorene and find its use in gas sensors and electronic devices owing to its extremely high carrier mobility. In the current work, we deployed stable α-AsP as a base material for the detection of formaldehyde and acetaldehyde. Initially, the stability and the electronic properties of the bare α-AsP are confirmed based on formation energy, ab initio molecular dynamics, phonon band structure, band structure, and PDOS (projected density of states) map. The band gap of α-AsP is computed to be 2.042 eV. Furthermore, the interaction of formaldehyde and acetaldehyde on α-AsP is examined based on band gap, charge transfer, and adsorption energy. The adsorption energies are observed in the scope of −0.277 eV to −0.497 eV, which falls in the physisorption regime. In addition, the adsorption and desorption behaviour of formaldehyde and acetaldehyde can be tailored by applying external strain. Thus, based on the results, we suggest that the α-AsP monolayer is a suitable material for sensing the formaldehyde and acetaldehyde.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115162"},"PeriodicalIF":3.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143591441","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}

引用次数: 0

Double proton transfer in formic, thioformic and dithioformic acid dimers: An energetic, mechanistic and kinetic investigation 甲酸、硫代甲酸和二硫代甲酸二聚体中的双质子转移：能量、机理和动力学研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-03-03 DOI: 10.1016/j.comptc.2025.115164

Monu , Binod Kumar Oram , Ankita Kothari , Biman Bandyopadhyay

引用次数: 0

Electron and positron impact ionization cross sections of neutral molecular species dissociating from C4F7N and its mixtures 从C4F7N及其混合物解离的中性分子种的电子和正电子影响电离截面

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-03-03 DOI: 10.1016/j.comptc.2025.115148

D. Geetha, Dhanoj Gupta

{"title":"Electron and positron impact ionization cross sections of neutral molecular species dissociating from C4F7N and its mixtures","authors":"D. Geetha, Dhanoj Gupta","doi":"10.1016/j.comptc.2025.115148","DOIUrl":"10.1016/j.comptc.2025.115148","url":null,"abstract":"<div><div>The electron and positron impact ionization cross sections are reported for neutral fragments originating from C<sub>4</sub>F<sub>7</sub>N and their mixture with air, CO<sub>2</sub>, and N<sub>2</sub> using the Binary-Encounter Bethe (BEB) method and its variants, such as BEB-W and BEB-B. The neutral targets studied are HF, CO, CO<sub>2</sub>, COF<sub>2</sub>, CHF<sub>3</sub>, CF<sub>3</sub>, CF<sub>4</sub>, C<sub>2</sub>F<sub>4</sub>, C<sub>2</sub>F<sub>6</sub>, C<sub>3</sub>F<sub>6</sub>, C<sub>3</sub>F<sub>8</sub>, C<sub>4</sub>F<sub>6</sub>, C<sub>4</sub>F<sub>8</sub>, C<sub>4</sub>F<sub>10</sub>, CN, HCN, CFN, C<sub>2</sub>N<sub>2</sub>, C<sub>2</sub>FN, C<sub>2</sub>F<sub>3</sub>N, C<sub>3</sub>F<sub>3</sub>N, C<sub>3</sub>F<sub>4</sub>N, C<sub>3</sub>F<sub>5</sub>N molecules. The results for most of the targets for electron imapct ionization compare well with the available experimental and theoretical results. However, for most of the molecules, the estimates of positron impact ionization are the first attempt. The correlation of the maximum ionization cross section for both electrons and positrons with the polarizability and the number of electrons of the target gave a good correlation fit. The cross section data presented in this article are important for C<sub>4</sub>F<sub>7</sub>N plasma.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115148"},"PeriodicalIF":3.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143562352","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}

引用次数: 0

The role of quantum-confined boron nitride nanotubes in gas monitoring: Adsorption and detection of NO, NO₂, SO₂, and SO₃. 量子约束氮化硼纳米管在气体监测中的作用：吸附和检测NO、NO₂、SO₂和SO₃。

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-03-03 DOI: 10.1016/j.comptc.2025.115158

Hazem Abdelsalam , Mahmoud A.S. Sakr , Nahed H. Teleb , Ghada M. Abdelrazek , Omar H. Abd-Elkader , Qinfang Zhang

{"title":"The role of quantum-confined boron nitride nanotubes in gas monitoring: Adsorption and detection of NO, NO₂, SO₂, and SO₃.","authors":"Hazem Abdelsalam , Mahmoud A.S. Sakr , Nahed H. Teleb , Ghada M. Abdelrazek , Omar H. Abd-Elkader , Qinfang Zhang","doi":"10.1016/j.comptc.2025.115158","DOIUrl":"10.1016/j.comptc.2025.115158","url":null,"abstract":"<div><div>This study investigates finite-length boron nitride nanotubes (4ZHBN-NTs) constructed from quantum dots for selective gas sensing, focusing on NO, NO₂, SO₂, and SO₃. Adsorption energy calculations showed stable interactions, especially with SO₃ (−2.805 eV). Natural bond orbital (NBO) analysis revealed significant charge transfer during adsorption, with NO₂ and SO₃ causing the highest electronic perturbations. Density of states (DOS) analysis confirmed strong gas-nanotube interactions through noticeable shifts in peak positions. Optical studies highlighted redshifts in absorption spectra, particularly for NO₂, with wavelengths extending up to 418 nm. Recovery time analysis revealed fast desorption for NO and NO₂, while SO₃ exhibited prolonged retention due to its higher adsorption energy. These findings demonstrate the high sensitivity of 4ZHBN-NTs to gas adsorption, with distinct electronic and optical signatures for each gas, showcasing their potential as efficient sensors for environmental monitoring.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1247 ","pages":"Article 115158"},"PeriodicalIF":3.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143534928","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}

引用次数: 0