Computational and Theoretical Chemistry最新文献

{"title":"Theoretical study on the effect of H2O on the formation mechanism of NOx precursor during 2-pyrrolidone pyrolysis","authors":"Chen Zhang ,&nbsp;Jun Shen ,&nbsp;Zhenqing Han ,&nbsp;Yun Guo ,&nbsp;Sha Wang ,&nbsp;Haiyong Peng ,&nbsp;Shengxiang Deng ,&nbsp;Jiaxun Liu","doi":"10.1016/j.comptc.2025.115510","DOIUrl":"10.1016/j.comptc.2025.115510","url":null,"abstract":"<div><div>The nitrogen in the pyrolysis process of kitchen waste partially originates from proteins (amino acids), and 2-pyrrolidone is a product with high content of glutamic acid. Density functional theory (DFT) was used to study the effect of H₂O on NO_x precursors (NH₃, HCN, HNCO) produced by the pyrolysis of 2-pyrrolidone. Compared with the reaction without H₂O, the reaction path and the results of the product have changed in varying degrees. This study found that NH₃ is more prone to form than HCN, which was consistent with the phenomenon that the release of NH₃ was higher than that of HCN during pyrolysis. In addition, it was found that H₂O reduced the reaction energy barrier of NH₃ and HCN during the pyrolysis of 2-pyrrolidone, and promoted the formation of NH₃ and HCN.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115510"},"PeriodicalIF":3.0,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145154842","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":"ReaxFF reactive molecular dynamic simulation and density functional theory calculation of pyrolysis mechanism and electronic characteristic of lignin with the addition of plastics","authors":"Jiaming Wang ,&nbsp;Mengna Bai ,&nbsp;Wei Zhuang ,&nbsp;Shukun Wang ,&nbsp;Shijie Zhang ,&nbsp;Shouyin Cai ,&nbsp;Erguang Huo","doi":"10.1016/j.comptc.2025.115511","DOIUrl":"10.1016/j.comptc.2025.115511","url":null,"abstract":"<div><div>The pyrolysis mechanism of lignin dimers with the addition of low-density polyethylene and the electronic characteristics of lignin dimers were studied using ReaxFF reactive molecular dynamic simulation and density functional theory calculation. The effects of temperature and the lignin dimer type on the lignin and LDPE co-pyrolysis were analyzed, the electronic properties and reactivities of lignin dimers were explored. The results showed that the oxygen-containing intermediate products generated from the pyrolysis of lignin promote the degradation of LDPE, thereby increasing the yield of hydrocarbon products. Meanwhile, the radicals released by LDPE interact with the pyrolysis products of lignin, further accelerating the pyrolysis of lignin. The reactivities of three lignin dimers were order as: α-ether type&gt;β-aryl type&gt;β-ether type. The oxygen atoms of hydroxyl in lignin dimer molecules exhibited strong negative charges and became electrophilic attack targets during the co-pyrolysis process.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115511"},"PeriodicalIF":3.0,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145154900","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 study on the degradation of hydroxybenzophenones by hydroxyl radical in water: Microscopic reaction mechanism, kinetics, toxicity","authors":"Meichao Chen ,&nbsp;Mingxue Li ,&nbsp;Yuxin Zhou ,&nbsp;Yuhui Ma ,&nbsp;Nuan Wen ,&nbsp;Qingyuan Gu ,&nbsp;Ju Xie ,&nbsp;Yanan Zhang ,&nbsp;Maoxia He","doi":"10.1016/j.comptc.2025.115507","DOIUrl":"10.1016/j.comptc.2025.115507","url":null,"abstract":"<div><div>This study used the DFT M062X/6-311G (d, p) method to explain the microscopic reaction mechanism of hydroxyl radical (•OH) with four benzophenones at the molecular level. The results showed that the most favorable reaction mechanism is the radical adduct formation (RAF) reaction. The order of reaction rate constants is <em>K</em>_{•OH, BP1} (2.18 × 10⁹ M⁻¹ s⁻¹) &gt; <em>K</em>_{•OH, 2HB} (4.35 × 10⁸ M⁻¹ s⁻¹) &gt; <em>K</em>_{•OH, 4DHB} (1.23 × 10⁸ M⁻¹ s⁻¹) &gt; <em>K</em>_{•OH, 4HB} (7.08 × 10⁷ M⁻¹ s⁻¹). Based on this, we established a kinetic model to compare two advanced oxidation processes (AOPs). The results showed that the degradation efficiency of benzophenones by the UV/H₂O₂ process was 16.0–53.8 % higher than that of the Fenton method. The purpose of this study is to gain a deeper understanding of the basic principles of hydroxyl degradation of benzophenone derivatives, and to provide a theoretical reference for process selection in the actual sewage treatment process.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115507"},"PeriodicalIF":3.0,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145154901","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":"Hydration-dependent interaction of Na+, K+ with glycine: A comparative study of neutral and zwitterionic forms via DFT calculations","authors":"Guang-Hong Jiang,&nbsp;Yuan-Yi Li,&nbsp;Ren-Zhong Li","doi":"10.1016/j.comptc.2025.115509","DOIUrl":"10.1016/j.comptc.2025.115509","url":null,"abstract":"<div><div>This study employs ab initio calculations to probe glycine-Na⁺/K⁺ interactions in water clusters. The results reveal that Na⁺-glycine complexes transition from neutral to zwitterionic configurations at six water molecules, while K⁺ systems achieve this shift at four. Proton transfer analysis shows that hydration can reduce zwitterion formation energy barriers. Multimethod analyses (IGMH, AIM) reveal that the binding strength of glycine-Na⁺/K⁺ initially decreases with hydration, with the weakest interactions occurring at the structural pre-transition stage from the neutral to the zwitterionic form. Energy decomposition analysis quantifies the dominan of electrostatic interactions. These results elucidate hydration-modulated amino acid-ion coordination dynamics critical for biological transport processes.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115509"},"PeriodicalIF":3.0,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145118768","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":"Extended CC bond chain controlled luminescence behavior of novel ESIPT-active benzothiazole-based fluorophore in near-infrared region: A TD-DFT insight","authors":"Zexi Huang,&nbsp;Hua Fang","doi":"10.1016/j.comptc.2025.115503","DOIUrl":"10.1016/j.comptc.2025.115503","url":null,"abstract":"<div><div>Using density functional theory (DFT) and time-dependent DFT (TD-DFT), the excited state intramolecular proton transfer (ESIPT) mechanisms and luminescent properties of (E)-2-(3-(3-(benzo[<em>d</em>]thiazol-2-yl)-2-hydroxy-5-methylstyryl)-5,5-dimethylcyclohex-2-en-1-ylidene) malononitrile (BTCMN) and its derivatives were systematically investigated. Four BTCMN derivatives with varying intramolecular C<img>C bond chain, namely BTCMN-1, BTCMN-2, BTCMN-3 and BTCMN-4 were designed to comprehensively explore the impact of C<img>C bond chain length on BTCMN. The selected functional is very reasonable since the experimental absorption and fluorescence wavelengths are reproduced. Detailed analyses have shown that the intramolecular C<img>C bond chain length obviously affects the ESIPT process and photophysical properties. With the elongation of the C<img>C bond chain within the molecule, the excited state intramolecular hydrogen bond (IHB) weakens, the ESIPT barrier increases, and both absorption and fluorescence wavelengths shift red. Especially, the fluorescence wavelength achieves near-infrared region by extending the chain of intramolecular C<img>C bond. Our results can provide more useful information to further design ESIPT-based fluorescent probes for living cell imaging.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115503"},"PeriodicalIF":3.0,"publicationDate":"2025-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145118770","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":"Regulating the interaction mechanism of thiazole derivatives with mild steel through the conjugation effect: a combined DFT and MD simulation","authors":"Xiaotong Xiong,&nbsp;Wenjing Yang,&nbsp;Peide Han","doi":"10.1016/j.comptc.2025.115490","DOIUrl":"10.1016/j.comptc.2025.115490","url":null,"abstract":"<div><div>DFT calculations qualitatively and quantitatively reveal that increased charge accumulation at the 2-isobutylthiazole (IBT)/2-acetylthiazole (ACT) with Fe interface strengthens the bonding between heteroatom active sites and Fe atoms. ACT exhibits superior inhibition performance, with adsorption energies of −70.56 kcal/mol⁻¹ for ACT compared to −61.33 kcal/mol⁻¹ for IBT, attributed to its extended conjugation and the strongest Fe<img>O bonding energy (−1.08 eV). The interaction originates from π-d hybridization, where enhanced π/π* delocalization promotes orbital overlap with Fe d states, confirming that a parallel molecular orientation is most favorable. MD simulations under acidic conditions further demonstrate that both conjugation and active sites dictate the extent of π-d coupling. Greater surface coverage of ACT leads to a more compact and stable protective film that effectively blocks corrosive species. The results provide atomic level insights into the anticorrosion mechanism, which could help in understanding the organic-metal interface and designing more effective inhibitors.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115490"},"PeriodicalIF":3.0,"publicationDate":"2025-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145118771","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":"Exploring the hydrogen interaction on Zn12O12 nanocages: A first-principles study","authors":"Francisxavier Paularokiadoss ,&nbsp;Thayalaraj Christopher Jeyakumar ,&nbsp;Christian A. Celaya ,&nbsp;M. Solórzano ,&nbsp;Youghourta Belhocine ,&nbsp;Bouzid Gassoumi ,&nbsp;Sahbi Ayachi","doi":"10.1016/j.comptc.2025.115502","DOIUrl":"10.1016/j.comptc.2025.115502","url":null,"abstract":"<div><div>This study uses density functional theory (DFT) a powerful computational method, to analyze how the hydrogen molecules adsorb in the Zn₁₂O₁₂ nanocage, a promising material for lightweight hydrogen storage applications. The adsorption mechanism is primarily governed by the charge redistribution and polarization effect originating from Zn<img>O bonds, which induce preferential binding of H₂ molecules at Zn sites. Detailed electronic structure analysis, supported by Quantum Theory of Atoms in Molecules (QTAIM) and Non-covalent Interaction (NCI) calculations, reveals that these interactions are weakly <em>physisorption</em> yet highly stable, ensuring reversible adsorption. The compute average adsorption energy is approximately −0.04 eV per H₂ molecule, indicating facile adsorption-desorption under ambient conditions. Zn₁₂O₁₂ nanocages demonstrate an impressive gravimetric hydrogen storage capacity exceeding 7.6 wt%, surpassing several current nanostructured materials. Furthermore, <em>ab initio</em> molecular dynamics (AIMD) simulations conducted at 300 K confirm the structural stability of Zn₁₂O₁₂ during H₂ adsorption. To further enhance the tunability of Zn₁₂O₁₂ nanocage properties for hydrogen storage applications, alkali metal doping (Li, Na, K) was investigated by substituting a Zn atom with an alkali element. Structural optimization and stability assessments confirm that the doped nanocages preserve their geometric integrity, while molecular electrostatic potential (MEP) analysis reveals pronounced localized charge redistribution around the dopant site. Although the computed average H₂ adsorption energies remain comparable to the pristine nanocage, the induction of alkali dopants generates chemically active regions that could facilitate tailored surface reactivity, enhance spillover processes, and enable applications specific functionalization. These findings provide deep insights into the H₂ retention mechanisms within Zn₁₂O₁₂ clusters, highlighting their versatility and potential for next-generation hydrogen energy systems.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115502"},"PeriodicalIF":3.0,"publicationDate":"2025-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145154835","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 insights into the adsorption and self-assembly of charged copolypeptides on silica","authors":"Nitin Kumar Singh,&nbsp;Mithun Radhakrishna","doi":"10.1016/j.comptc.2025.115479","DOIUrl":"10.1016/j.comptc.2025.115479","url":null,"abstract":"<div><div>This study explores the molecular mechanisms driving peptide-silica interactions, focusing on the adsorption and self-assembly of lysine-leucine copolypeptides and their influence on lysozyme adsorption. Using classical, long-timescale molecular dynamics (MD) simulations, we examine how charge density and sequence blockiness affect peptide behavior on negatively charged silica surfaces. Poly-lysine homopolypeptides show strong electrostatic interactions, leading to full surface adsorption, while neutral poly-leucine peptides weakly adsorb and orient perpendicularly. Copolypeptides with a fixed charge density of 0.5 exhibit blockiness-dependent adsorption and structural organization. Increased blockiness promotes independent peptide behavior and varied self-assembly. Modified silica surfaces functionalized with these peptides enhance lysozyme stability and reduce conformational disruption compared to bare silica. Our findings demonstrate that peptide sequence design can modulate surface interactions and protein adsorption. This work provides valuable insights into engineering amphiphilic polypeptides for surface functionalization, with potential applications in biomaterials, biosensing, and therapeutic delivery systems.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115479"},"PeriodicalIF":3.0,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145096964","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":"Assessing accelerated reaction network exploration with ChemTraYzer-TAD and PESmapping","authors":"F. Schmalz ,&nbsp;E.L. Mudimu ,&nbsp;I. Chair ,&nbsp;W.A. Kopp ,&nbsp;K. Leonhard","doi":"10.1016/j.comptc.2025.115461","DOIUrl":"10.1016/j.comptc.2025.115461","url":null,"abstract":"<div><div>Developing chemical combustion mechanisms for novel bio- and e-fuels is a challenge, given that many established mechanism analogies originate from fossil fuels. This work studies the ability of two new reaction network exploration methods, ChemTraYzer-TAD and PESmapping, to suggest potentially important reaction paths to combustion mechanisms, highlighting the differences and similarities of the two methods. In the reaction space of ethyl-2-yl formate radical combustion, all expected important reactions are found, while many new reactions are detected by one of the two methods. This shows that the combination of the two methods provides an optimal exploration result, <em>i.e.</em>, detection of both expected and novel reaction pathways.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115461"},"PeriodicalIF":3.0,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145154836","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":"Ɣ-Graphyne as a possible candidate for Li+, Na+, and K+ metal ion battery anode","authors":"V. Ludwig,&nbsp;F. Sato,&nbsp;A.B. Morais,&nbsp;A.C.M. Carvalho","doi":"10.1016/j.comptc.2025.115496","DOIUrl":"10.1016/j.comptc.2025.115496","url":null,"abstract":"<div><div>A systematic theoretical study employing Density Functional Theory (DFT) approaches has been conducted to investigate the interaction of alkali ions Li⁺, Na⁺, and K⁺ with the GY surface. Interaction energies, charge transfer mechanisms, and cell voltage values were modeled using high-level DFT calculations with the cam-B3LYP and PBE functionals. Both cluster and periodic boundary condition models were employed to provide a more comprehensive understanding of the phenomena under investigation. This combined approach leverages the strengths of both models, offering a deeper insight into the structural.</div><div>and electronic properties of the material. Adsorption of each ion on the GY surface was examined at various positions, revealing a preference for adsorption at the center of the GY triangular structure, with calculated adsorption energies ranging from −2.98 to −1.69 eV. Notably, the periodic model yielded adsorption energies that were approximately 30–45 % higher (more stable) compared to the cluster model. Furthermore, our results demonstrate that the band gap energy can be tuned by varying the relative position of the ions with respect to the GY surface. Finally, an analysis of the cell voltage values was performed to evaluate the potential of the GY allotrope as an anode material for ion batteries.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115496"},"PeriodicalIF":3.0,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145118769","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}