Chemical Physics最新文献

{"title":"The self-trapped holes in AlP:KH₂PO₄ crystals: A DFT + U description","authors":"Jianghai Wang ,&nbsp;Tingyu Liu ,&nbsp;Wei Hong ,&nbsp;Zehao Feng ,&nbsp;Huifang Li ,&nbsp;Xu Lu","doi":"10.1016/j.chemphys.2025.112942","DOIUrl":"10.1016/j.chemphys.2025.112942","url":null,"abstract":"<div><div>The self-trapped hole (STH) caused by the defect Al substituting for P (Al_P) in KH₂PO₄ (KDP) crystals have been studied by Density functional theory (DFT) + <em>U</em> and the bond distortion method (BDM). The STH is localized mainly on two O atoms in the lattice, with a shape characteristic of an O <em>2p</em> orbital and STHs can stably exist in this system. The STHs introduce isolated defect states (O <em>2p</em>) in the bandgap and generate an absorption spectrum peaking at 313 nm., which is consistent with experimental results. The defect transformation level of STH is in the bandgap, which can assist multi-photon absorption, thereby reducing laser-induced damage threshold (LIDT).</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112942"},"PeriodicalIF":2.4,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046262","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":"First-principles study of differences in flotation behavior of quartz and muscovite","authors":"Wencheng Li ,&nbsp;Zhijun Ma ,&nbsp;Xingyuan Weng ,&nbsp;Yunsheng Zheng ,&nbsp;Hao Guo ,&nbsp;Huiling Xing ,&nbsp;Zhuomin Li ,&nbsp;Linfeng Cheng","doi":"10.1016/j.chemphys.2025.112943","DOIUrl":"10.1016/j.chemphys.2025.112943","url":null,"abstract":"<div><div>The flotation separation of quartz and muscovite, typical silicate minerals, is a notable challenge in mineral processing. Herein, first-principles calculations were employed to elucidate the fundamental causes of the differences between the flotation behaviors of the two minerals at the atomic scale. The electron transfer, chemical bonding information, projected density of states, and charge difference density of the two minerals were calculated through density functional theory and compared. The results suggest that quartz contains only Si<img>O strongly polar covalent bonds, whereas the structure of muscovite is dominated by Si<img>O covalent bonds, with the substitution of Si⁴⁺ with Al³⁺ introducing ionic Al<img>O bonds. At the same time, K⁺ in the interlayer compensates for the charge imbalance through pure ionic bonds. The computed adsorption energies of the cationic trapping agent dodecyl amine on quartz and muscovite were −2.103 and −5.879 kcal/mol, respectively, which is a notable difference. In line with the findings of flotation studies, this suggests that dodecyl amine can be adsorbed on both quartz and muscovite, but the adsorption is stronger on muscovite.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112943"},"PeriodicalIF":2.4,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046264","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":"Understanding the nucleophilicity of para-substituted anilines in methanol: reactivity and computational analyses","authors":"Amira Ghabi ,&nbsp;Rim Hamdi ,&nbsp;Amel Hedhli ,&nbsp;Jean-François Longevial ,&nbsp;Michéle Sindt ,&nbsp;Sahbi Ayachi ,&nbsp;Taoufik Boubaker","doi":"10.1016/j.chemphys.2025.112934","DOIUrl":"10.1016/j.chemphys.2025.112934","url":null,"abstract":"<div><div>We investigated the nucleophilic reactivity of a series of para-substituted anilines <strong>2a-2e</strong> through a combined kinetic and theoretical approach, employing their reactions with thiophenes <strong>1a-1c</strong> as electrophilic references in methanol at 20 °C. The satisfactorily correlations observed between the reaction rates and the oxidation potentials of the anilines provide compelling evidence for a single-electron transfer (SET) mechanism. Nucleophilicity parameters (<em>N</em>, s_N) were determined in methanol following Mayr's empirical eq. A particularly compelling finding of our study is the good correlation observed between the nucleophilicity parameters (<em>N</em>) of anilines <strong>2a-2e</strong> measured in methanol and those reported by Mayr in acetonitrile, demonstrating the role of solvent polarity in nucleophilic reactivity. Utilizing this correlation and the established relationship between <em>N</em> and the Hammett constant (σ_p), we predicted <em>N</em> values for five additional 4-X-anilines <strong>2f-2j</strong> (X = NO₂, CN, CF₃, F, and N(CH₃)₂). In addition, density functional theory (DFT) transition-state (TS) analyses provided activation free energies (ΔG^≠) for each para-substituent (X = OH, OCH₃, CH₃, H, Cl), all confirmed by a single imaginary frequency along the reaction coordinate. The computed ΔG^≠ values inversely correlate with N: electron-donating groups decrease, and electron-withdrawing groups increase the activation barrier. Furthermore, DFT calculations were conducted to explore relationships between <em>N</em> and various reactivity descriptors, including the global nucleophilicity index (ω⁻¹), dipole moment (μ), polarizability (α), and hyperpolarizability (β) for the ten para-X-substituted anilines <strong>2a-2j</strong>. The data reveal a clear structure–property framework for tuning the NLO response of substituted anilines. Molecules substituted with strong EWGs are superior candidates for NLO applications due to their high dipole moments, elevated polarizabilities, and exceptionally large hyperpolarizabilities.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112934"},"PeriodicalIF":2.4,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046266","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 Iron Phthalocyanine sheets via density functional theory: Mechanical, electronic, and optical characteristics","authors":"Roya Majidi ,&nbsp;Ahmad.I. Ayesh","doi":"10.1016/j.chemphys.2025.112944","DOIUrl":"10.1016/j.chemphys.2025.112944","url":null,"abstract":"<div><div>This study explores a two-dimensional material based on iron phthalocyanine, termed as FePc sheet. The structural, electronic, mechanical, and optical characteristics of this sheet are explored using density functional theory. The results confirm that the FePc sheets are energetically highly favorable and mechanically stable. Its mechanical behavior and anisotropic properties are shown by calculating Young's modulus as well as Poisson's ratio. Findings suggest that the FePc sheet could be a promising candidate for use in nanoscale devices or systems that require a delicate or less rigid material. The electronic analysis indicates the metallic and magnetic nature for this sheet. Additionally, the optical parameters including the dielectric function, optical conductivity, refractive index, absorption coefficient, reflection, and transmission coefficients over a range of photon energies are studied. The results point to the potential use of this sheet in optoelectronic devices as well as energy harvesting systems.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112944"},"PeriodicalIF":2.4,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046261","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 study on the C(sp3)-H Silylation of N-benzyl-N-ethylethanamine catalyzed by B(C6F5)3","authors":"Lu-jia Zhong,&nbsp;Tian-Tian Feng,&nbsp;Qin Xiao,&nbsp;Da-Gang Zhou,&nbsp;Li-Jun Yang","doi":"10.1016/j.chemphys.2025.112935","DOIUrl":"10.1016/j.chemphys.2025.112935","url":null,"abstract":"<div><div>The mechanisms for the Csp³-H silylation of <em>N</em>-benzyl-<em>N</em>-ethylethanamine have been investigated by employing the M06-2×-D3/ma-def2-TZVP level. The SMD method, based on solute electron density, was used to simulate the solvent of <em>p</em>-xylene. Computational results reveal that B(C₆F₅)₃ as the catalyst can help to finish the Csp³-H activation; moreover, B(C₆F₅)₃ and <em>N</em>-benzyl-<em>N</em>-ethylethanamine can complete the conversion from <em>N</em>-benzyl-<em>N</em>-ethylethanamine to alkene derivative, which can reacts with the protonated diphenylsilane to get the adding intermediate. Finally, there are two paths (a and b) that could yield the final product the 1-benzyl-4,4-diphenyl-1,4-azasilinane. The Gibbs free energy profile concludes that path b2 with lower energy barrier is optimal. The calculations could provide valuable insights for understanding similar reactions and developing new C(sp³)-H silylation.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112935"},"PeriodicalIF":2.4,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046263","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":"Single-phase white-emitting phosphors based on Eu2+-activated apatite-type Ba5(PO4)3Cl induced by (BO3)3− diadochic substitution","authors":"Tao Zhao,&nbsp;Lu Xie,&nbsp;Fenzhong Long,&nbsp;Fangui Meng,&nbsp;Jin Han,&nbsp;Xinmin Zhang","doi":"10.1016/j.chemphys.2025.112936","DOIUrl":"10.1016/j.chemphys.2025.112936","url":null,"abstract":"<div><div>White-light emission with a single activator in a single host is an attractive function of phosphors. In this work, we investigated the photoluminescence properties of Ba₅(PO₄)_3-x(BO₃)_xCl, which is a compound derived from apatite type Ba₅(PO₄)₃Cl by means of diadochic substitution, with Eu²⁺-activation using photoluminescence measurements. Phosphors show a tunable emission from deep blue to white and then orange under near ultraviolet light excitation. In the compound Ba₅(PO₄)₃Cl, Ba²⁺ ions occupy two crystallographically distinct sites; only one site is preferential site for Eu²⁺ substitution. Through introducing (BO₃)³⁻ group into the host lattice, additional emission peak is observed. Decay analysis indicates that the second emission is generated by Eu²⁺ at another crystallographic site caused by the introducing of (BO₃)³⁻ group. A phosphor-converted light-emitting diode has been successfully fabricated with the incorporation of an as-prepared Ba_4.96(PO₄)_2.6(BO₃)_0.4Cl:0.04Eu²⁺ phosphor and a 365 nm near-ultraviolet chip, which exhibits Commission International de I'Eclairage chromaticity coordinates of (0.3151, 0.3695) and a correlated color temperature of 6173 K. These findings provided a new way for preparing white light phosphors by doping a single activator in a single component.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112936"},"PeriodicalIF":2.4,"publicationDate":"2025-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145020183","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":"Examination of the applicability of multicomponent quantum mechanics to infrared spectroscopy calculations","authors":"Kazuki Kataoka,&nbsp;Yusuke Kanematsu,&nbsp;David S. Rivera Rocabado,&nbsp;Takayoshi Ishimoto","doi":"10.1016/j.chemphys.2025.112937","DOIUrl":"10.1016/j.chemphys.2025.112937","url":null,"abstract":"<div><div>Quantum mechanics (QM) calculations of infrared spectra based on the Born–Oppenheimer and harmonic oscillator approximations cause errors depending on the level of the electronic structure calculation and the anharmonicity of the potential energy surface. Errors owing to anharmonicity are particularly strong for vibrations involving hydrogen nuclei with large quantum fluctuations. A possible solution to this issue is to apply multicomponent QM (MC_QM), which extends conventional QM calculations to quantum MC systems to enable the analysis of H/D isotope effects by treating nuclei as quantum particles, such as electrons. To investigate the suitability of MC_QM for infrared spectroscopy, this study calculated the vibrational frequencies of several H/D substituents using conventional QM and MC_QM methods and compared them with the corresponding experimental values. Results demonstrate that the MC_QM values exhibit improved reproducibility compared to the experimental values by incorporating nuclear quantum effects.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112937"},"PeriodicalIF":2.4,"publicationDate":"2025-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145010718","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":"Enhancing the energy release and combustion performance of nanothermites through the introduction of GO","authors":"Jingjing Wang ,&nbsp;Xin Lu ,&nbsp;Shuang Zuo ,&nbsp;Dawei Li ,&nbsp;Kangzhen Xu","doi":"10.1016/j.chemphys.2025.112938","DOIUrl":"10.1016/j.chemphys.2025.112938","url":null,"abstract":"<div><div>Al/GO/CoWO₄ were prepared by a self-assembly method and the introduction of GO can effectively weaken the agglomeration of nanoparticles and improve the ignition performance. The different <em>Φ</em> and GO contents were adjusted to investigate the optimum performance. Al/GO/CoWO₄ shows a tight layered stacking structure and the energy release can reach 2500–3300 J·g⁻¹, much higher than those of Al/CoWO₄ (3064 J·g⁻¹) and Al/Co₃O₄ (2084 J·g⁻¹). Al/GO-7.5 wt%/CoWO₄(<em>Φ</em> = 1.50) has the largest energy release (3249 J·g⁻¹) and Al/GO-7.5 wt%/CoWO₄(Φ = 1.75) has the largest flame area, the shortest burning time (7 ms) and ignition delay time (2 ms) among all, indicating that the excess Al contributes to the full combustion of nanothermite reaction. The DSC results show the superior catalytic performance on ammonium perchlorate (AP) and cyclotrimethylenetrini-tramine (RDX). The results indicate the outstanding combustion and catalytic performance of Al/GO/CoWO₄</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112938"},"PeriodicalIF":2.4,"publicationDate":"2025-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046260","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":"Mechanisms of high-temperature inhibition of montmorillonite surface hydration by polyethyleneimine additives","authors":"Jiafang Xu ,&nbsp;Lingfeng Kong ,&nbsp;Jie Chen ,&nbsp;Justine Kiiza ,&nbsp;Shi Yuan","doi":"10.1016/j.chemphys.2025.112932","DOIUrl":"10.1016/j.chemphys.2025.112932","url":null,"abstract":"<div><div>The hydration swelling of clay minerals during oil and gas production can severely compromise wellbore stability, particularly under deep, high-temperature, and high-pressure conditions, where the thermal limitations of drilling fluids exacerbate downhole accidents. This study employs molecular dynamics (MD) simulations to investigate the interactions between water molecules, clay, and polyethyleneimine (PEI) under high-temperature and high-pressure conditions. Key parameters, including dynamic parameters, hydration characteristics, adsorption conformations of water, Na⁺, and PEI, and intermolecular interaction energies, were analyzed to elucidate how PEI molecules inhibit montmorillonite surface hydration. The results reveal that PEI primarily hinders hydration through Coulombic interactions and hydrogen bonding with the Na-montmorillonite surface, with inhibition significantly declining above 473 K. Functional groups like -NH₂ and -OH enhance PEI adsorption at high-temperature, while -SO₃⁻ and -COO⁻ groups improve both the hydration resistance of PEI and its disruption of the montmorillonite hydration layer at high-temperature. These findings provide a theoretical basis for the design of shale inhibitors in high-temperature drilling fluids and offer insights into the underlying mechanisms. The research has significant implications for developing drilling fluids capable of maintaining stability under high-temperature conditions.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112932"},"PeriodicalIF":2.4,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145027469","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":"Highly efficient photocatalytic hydroxylation of benzene by a novel Fenton-like system: Cu/Mn bimetallic MOF derived carbon-supported materials","authors":"Xu Jia ,&nbsp;Jiaqi Zhang ,&nbsp;Jiaolong Qiao ,&nbsp;Zhiqi Song ,&nbsp;Liuxue Zhang ,&nbsp;Xiulian Wang ,&nbsp;Shuyan Jiao ,&nbsp;Guomin Yu ,&nbsp;Kefan Dai","doi":"10.1016/j.chemphys.2025.112924","DOIUrl":"10.1016/j.chemphys.2025.112924","url":null,"abstract":"<div><div>To enhance the yield of phenol preparation while improving photocatalyst stability and photocatalytic performance, Cu/Mn-MOF with varying Cu/Mn ratios were synthesized via a solvothermal method. The optimal Cu/Mn-MOF were subsequently calcined to obtain carbon-supported composites (denoted as Cu/Mn-MOF@C). Experimental results demonstrated that the phenol yield reached 20.35% after 4 h of photocatalytic benzene hydroxylation using Cu/Mn-MOF@C. Furthermore, the composite exhibited excellent recyclability, with no significant decline in phenol yield observed over five consecutive reaction cycles, while maintaining robust photocatalytic activity. These results suggested that the carbon-supported materials developed in this study hold significant potential for applications in photocatalytic phenol production and provide valuable insights for designing high-efficiency photocatalysts.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112924"},"PeriodicalIF":2.4,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145010714","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}