Chemical Physics最新文献

{"title":"DFT study of the influence of Chalcogen substitution on the structural, mechanical, thermodynamic, magnetic, and electronic properties of Ag₃FeX₄ (X = S, Se, Te)","authors":"Abdalla Obeidat,&nbsp;Saleh Abu-Rajouh,&nbsp;Mohammad-Khair Qaseer","doi":"10.1016/j.chemphys.2025.112857","DOIUrl":"10.1016/j.chemphys.2025.112857","url":null,"abstract":"<div><div>We investigated the structural, mechanical, and electronic properties of Ag₃FeX₄ (X = S, Se, Te) chalcogenides using density functional theory with PBE and PBE + U functionals. The compounds crystallize in a cubic P-43 m structure, showing systematic lattice expansion from 5.975 Å (S) to 6.423 Å (Te). Cohesive energy calculations reveal Ag₃FeS₄ as the most stable, with superior mechanical properties (bulk modulus = 22.87 GPa, shear modulus = 6.99 GPa), while Ag₃FeTe₄ exhibits greater ductility. Phonon dispersion confirms dynamical stability, with Debye temperatures decreasing from 149.3 K to 91.3 K, correlating with thermal conductivity variations. Magnetic properties demonstrate ferromagnetic ordering (∼3 μB) dominated by Fe 3d states, preserved under Hubbard U corrections. Electronic structure analysis shows metallic conductivity arising from Fe 3d-chalcogen p hybridization, unaffected by U corrections. The combination of metallic behavior, mechanical anisotropy, and thermal stability suggests potential applications in spintronics and thermoelectrics.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112857"},"PeriodicalIF":2.0,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144631372","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":"Global potential energy surface for the ground state of H2O− and dynamics studies of the O− + H2 → H + OH− reaction","authors":"Limei Xu,&nbsp;Yanli Wang,&nbsp;Wentao Li","doi":"10.1016/j.chemphys.2025.112850","DOIUrl":"10.1016/j.chemphys.2025.112850","url":null,"abstract":"<div><div>A new potential energy surface (PES) of the ground state (1² <em>A</em>′) of H₂O⁻ system is constructed using permutation invariant polynomial neural network based on 22,983 <em>ab initio</em> energy points. To improve the quality of PES, the Davidson correction was considered in the calculations and the basis sets were extrapolated to the complete basis set limit. The spectroscopic constants of the diatoms were obtained from the new PES and compared with available experimental values. The results indicate that present values are in good agreement with experimental data. The topographical properties of the new PES are also examined in detail. To further test the accuracy of PES, the dynamics calculations of the O⁻ + H₂ → H + OH⁻ reaction are performed. The reaction probabilities, integral cross sections and rate constants are calculated and compared with available theoretical and experimental values in the collision energy range from 0.01 to 1.0 eV.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112850"},"PeriodicalIF":2.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144614645","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":"Decomposition mechanism of isoprenoid p-cymene during supercritical water gasification by ReaxFF simulation","authors":"Yutong Wang ,&nbsp;Shan Hua ,&nbsp;Junhao Guo ,&nbsp;Xi Chen ,&nbsp;Yajie Tian ,&nbsp;Kangjun Wang","doi":"10.1016/j.chemphys.2025.112845","DOIUrl":"10.1016/j.chemphys.2025.112845","url":null,"abstract":"<div><div>Isoprenoid <em>p</em>-cymene exhibits severe coking tendency during pyrolysis, restricting its conversion efficiency when served as biofuels. However, this is expected to be mitigated through supercritical water gasification (SCWG), a clean and sustainable conversion technology. In this study, ReaxFF simulations are employed to investigate the SCWG process of <em>p</em>-cymene at 2800 K. Due to the participation of H₂O, H-abstractions occur more frequently in the initial decomposition. Subsequent reactions of H₂O with generated C₁₀H₁₉, C₉H₁₇, and C₇H₁₃ radicals, thereby effectively inhibit coke formation by decomposing those existing coking precursors and preventing their further chain-transfer reactions. Meanwhile, Species-dependent analysis on generation channels of CO and H₂ suggest that reactions involving H₂O also actively promote the conversion of less reactive C in the aromatic structure. This computational study could deepen the understanding of decomposition of aromatic isoprenoids during pyrolysis and SCWG process and offers potential solutions for enhancing the conversion efficiency of isoprenoid biofuels.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112845"},"PeriodicalIF":2.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604851","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 pressure induced innovations in the essential physical properties of niobium based perovskite oxides: A first principles analysis","authors":"Shahid Iqbal ,&nbsp;Shafaat Hussain Mirza ,&nbsp;Muhammad Adnan Samhi ,&nbsp;Salah Knani ,&nbsp;Amna Parveen","doi":"10.1016/j.chemphys.2025.112855","DOIUrl":"10.1016/j.chemphys.2025.112855","url":null,"abstract":"<div><div>Perovskite oxides particularly ZNbO₃ (Z = Na, K), are promising candidates due to their tunable optoelectronic properties. Analysis of the electronic band structure reveals that both compounds exhibit indirect bandgaps, which expand from 1.284 eV to 1.830 eV for NaNbO₃ and from 1.489 eV to 1.814 eV for KNbO₃ as pressure rises from 0 to 50 GPa. Optical properties reveal notable absorption in the UV region, improved reflectivity peaks, and robust optical conductivity. Powder XRD patterns manifest peak shifts towards higher angles with rising pressure, showing the lattice compression and improved crystalline quality, notably in KNbO₃. According to Pugh's and Poisson's ratio investigations, the materials exhibit anisotropic behavior and predominantly ductile characteristics. Thermodynamic properties of ZNbO₃ (Z = Na, K) are also evaluated to check these materials dynamical stability and appropriateness in thermal applications. As a result, the ZNbO₃ (Z = Na, K) perovskites exhibit suitability broadly tunable phosphor materials for energy-efficient white LED devices.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112855"},"PeriodicalIF":2.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144595381","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":"Helical and antiparallel structures from truncated long-range interactions in water and dipolar spins","authors":"Yoshiteru Yonetani","doi":"10.1016/j.chemphys.2025.112854","DOIUrl":"10.1016/j.chemphys.2025.112854","url":null,"abstract":"<div><div>It is known that dipolar systems such as water produce highly ordered layered structures when long-range dipolar interactions are truncated at a finite distance. However, many parts of this long-range phenomenon remain unsolved. Herein, we fundamentally explored this phenomenon using Monte Carlo simulations for dipolar spins and molecular dynamics simulations for water. The results show that the width of the layers does not depend on the system size but is determined by the cutoff length. At the same time, layer formation occurred even without periodic boundary conditions. These results suggest that layer formation is a consequence of cutoff rather than the periodic boundary conditions. We also found that water has a helical dipole distribution, whereas dipolar spin has an antiparallel distribution, with these two forms being energetically competing. Our findings on the relationship between long-range interactions and the resulting structures are expected to contribute to future explorations of structures with similar ordering in magnetic, dielectric, and soft materials.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112854"},"PeriodicalIF":2.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604850","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":"Studies on electrical properties of PLD grown BiFeO3 - based layered MFIS heterostructure device","authors":"Akshay Panchasara ,&nbsp;Urjitsinh Rathod ,&nbsp;Sumana Hajra ,&nbsp;Pruthaba Jadeja ,&nbsp;Akshay Ranpariya ,&nbsp;Savan Katba ,&nbsp;Vanaraj Solanki ,&nbsp;Mahesh Jivani ,&nbsp;Ashish Ravalia","doi":"10.1016/j.chemphys.2025.112851","DOIUrl":"10.1016/j.chemphys.2025.112851","url":null,"abstract":"<div><div>The pulsed lase deposited layered based thin film heterostructured device have been fabricated in Ag (metal) / Ca doped BiFeO₃ (Ferroelectric) / SrTiO₃ (Insulator) / ZnO (Semiconductor) MFIS geometry on STO (100) single crystalline substrate. The X-ray diffraction measurement confirm the substrate-oriented growth of Ca doped BiFeO₃ and SrTiO₃ layer while growth of ZnO is in different geometry due to its different structure than substrate. Surface and microstructural characterization have been carried out using Atomic Force Microscopy measurements which indicates the homogenous grain growth of Ca doped BiFeO₃ and ZnO layer. Electrical properties of proposed Ca doped BiFeO₃ based MFIS heterostructure have been studied using frequency dependent dielectric, cyclic I-V behaviour (with and without UV illumination) and channel resistance measurements. To understand the electrical property of proposed device, various charge conduction mechanism has understood using the fitting of I-V data. In addition, role of Ca doped BiFeO₃ ferroelectric layer in the channel resistance is investigated.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112851"},"PeriodicalIF":2.0,"publicationDate":"2025-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144634142","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":"HTS/FTIR investigations in the spectral range 4000–600 cm−1 and BET method of specific surface area of various montmorillonite clays modified by monocationic and dicationic imidazolium ionic liquids","authors":"A. Ahmed ,&nbsp;W.A.A. Ahmed ,&nbsp;T. Moumene ,&nbsp;El H. Belarbi ,&nbsp;V. Baeten ,&nbsp;S. Bresson","doi":"10.1016/j.chemphys.2025.112844","DOIUrl":"10.1016/j.chemphys.2025.112844","url":null,"abstract":"<div><div>Three different types of montmorillonite, K10, KSF, and SWy-3, were analyzed using HTS/FTIR spectroscopy. The HTS/FTIR spectra revealed two spectral regions (3800–2600, 2000–1000 cm⁻¹), highlighting the vibrational signatures that differentiate the three types of clays. The vibrational study of the three types of clays modified with two ionic liquids ([EMIM⁺][I⁻] monocationic ionic liquid and [M(CH₂)IM²⁺][2I⁻] dicationic ionic liquid) revealed several vibrational changes directly related to the presence of the ionic liquids in the clays. On one hand, the transition from monocationic to dicationic ionic liquids intercalated into the clay structure significantly affected the HTS/FTIR spectra. On the other hand, the HTS/FTIR spectra of SWy-3 show more significant vibrational changes than those of the other two clays after the intercalation of ionic liquids. To complement these results, a study of the specific surface area of these clays and these clays modified by the [M(CH₂)IM²⁺][2I⁻] dicationic ionic liquid using the BET method is presented.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112844"},"PeriodicalIF":2.0,"publicationDate":"2025-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144654659","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":"Scattering of N2 molecules from tungsten surfaces: crystallographic anisotropy effects in the energy exchanges","authors":"Maria Rutigliano ,&nbsp;Fernando Pirani","doi":"10.1016/j.chemphys.2025.112838","DOIUrl":"10.1016/j.chemphys.2025.112838","url":null,"abstract":"<div><div>Elastic and inelastic scattering of nitrogen molecules from tungsten surfaces is studied to understand how crystallographic anisotropy affects the dynamics of fundamental elementary processes involving energy exchange during the collisions that occur under a variety of conditions of applied interest. Gaseous nitrogen molecules, in well-defined low-lying roto-vibrational states and at low-medium collision energies, impinge on two different crystallographic planes of the W surface: (100) and (110). A recently proposed Potential Energy Surface, which accurately accounts for the long-range non-covalent interactions promoting physisorption, has been used in the simulations. It has been found that reflection from the two surface orientations occurs through both direct and indirect mechanisms, with the latter being dominant at low collision energies. The vibrational state of the molecules is preserved after interacting with the gas surface, while significant anisotropy is observed in the behavior of the rotational distributions of the scattered molecules.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112838"},"PeriodicalIF":2.0,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144595383","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":"RbNbX₃ (X = cl, Br, I) lead-free halide perovskites: A DFT study of structural, elastic, electronic, and thermoelectric properties for energy applications","authors":"Blaha Lamia Farah ,&nbsp;Khatir Radja ,&nbsp;Ameri Ibrahim ,&nbsp;Kessairi Khadra ,&nbsp;Ameri Mohammed ,&nbsp;Y. Al-Douri","doi":"10.1016/j.chemphys.2025.112843","DOIUrl":"10.1016/j.chemphys.2025.112843","url":null,"abstract":"<div><div>The search for stable lead-free perovskites has gained significant attention as a promising solution to address the toxicity and instability challenges of lead-based counterparts. This investigation comprehensively examines rubidium-based cubic halide perovskites RbNbX₃ (X = Cl, Br, I) using first-principles calculations within the density functional theory framework. Through the full-potential linearized augmented-plane-wave (FP-LAPW) method implemented in WIEN2k, we systematically analyze the structural, elastic, mechanical, electronic, magnetic, and thermoelectric properties. Structural optimization via the Birch-Murnaghan equation of state confirms cubic symmetry with lattice parameters of 5.2049 Å, 5. 4918 Å and 5.8665 Å for RbNbX₃ (X = Cl, Br, I), respectively, and reveals a stable ferromagnetic ground state. Electronic structure calculations using the modified Becke-Johnson (mBJ) potential demonstrate semiconducting behavior with indirect band gaps of 1.023 eV (Cl), 0.866 eV (Br), and 0.710 eV (I), accompanied by a consistent total magnetic moment of ∼3 μB predominantly originating from Nb-4d orbitals. Densities of states are calculated to predict the interaction of orbitals of distinct atoms in the compounds. Mechanical stability is confirmed through elastic constant analysis, with RbNbCl₃ and RbNbBr₃ exhibiting brittle characteristics while RbNbI₃ shows ductile behavior based on Pugh's ratio evaluation. Thermoelectric analysis confirms that RbNbX₃ perovskites exhibit excellent potential for energy conversion applications, demonstrating peak ZT values of 0.99 (100<em>K</em>) for RbNbI₃, 0.86 (500 K) for RbNbBr₃, and 0.8 (900 K) for RbNbCl₃. These high figures of merit arise from their superior Seebeck coefficients (up to 2917 μV/K) and low thermal conductivity. All these findings establish RbNbX₃ perovskites as promising candidates for spintronic and other advanced energy technologies, all within an environmentally friendly framework.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112843"},"PeriodicalIF":2.0,"publicationDate":"2025-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144595382","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":"Reaction mechanism of methanol on 4H-SiC substrate surface: a density functional theory study","authors":"Jiayu Zhang,&nbsp;Jianlin Sun,&nbsp;Erchao Meng,&nbsp;Daoxin Su,&nbsp;Qianhao Chang","doi":"10.1016/j.chemphys.2025.112849","DOIUrl":"10.1016/j.chemphys.2025.112849","url":null,"abstract":"<div><div>In this study, density functional theory (DFT) methods were employed to systematically investigate the adsorption, dissociation, and subsequent reaction pathways of methanol molecules (CH₃OH) on the C-terminated surface and Si-terminated face of silicon carbide (SiC) cluster models. By optimizing geometric structures, tracing reaction pathways and transition states, analyzing electronic density of states, strong and weak interactions, and bond orders, the detailed reaction mechanisms of methanol molecules on different surfaces of SiC were revealed. The research found that methanol molecules undergo dissociative adsorption on both the Si-terminated surface and C-terminated surface of SiC, with two dissociative pathways existing due to variations in adsorption sites or external conditions. The Si-terminated surface is more reactive compared to the C-terminated surface. These findings provide atomistic insights into surface reactivity, guiding the design of non-aqueous slurries for efficient SiC chemical mechanical polishing (CMP).</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112849"},"PeriodicalIF":2.0,"publicationDate":"2025-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144580991","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}