Chemical Physics最新文献

{"title":"Thermally stable 2D AlTlF4: A combined DFT and AIMD study of structural, electronic, thermal, and optical properties","authors":"Yousif Hussein Azeez ,&nbsp;Nzar Rauf Abdullah","doi":"10.1016/j.chemphys.2025.112980","DOIUrl":"10.1016/j.chemphys.2025.112980","url":null,"abstract":"<div><div>This study offers the first comprehensive investigation of the structural, electronic, thermal, and optical characteristics of the mixed metal fluoride AlTlF<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> by density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. The negative formation energy of -<span><math><mrow><mn>3</mn><mo>.</mo><mn>11</mn><mspace></mspace><mi>eV</mi></mrow></math></span> for AlTlF<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> signifies energetic stability, whereas phonon dispersion analysis demonstrates the lack of negative frequencies, thereby affirming its dynamic stability. Furthermore, the AIMD simulation confirms its thermal stability. Electronic structure simulations reveal a substantial indirect band gap of 5.42 eV (GGA) and 6.75 eV (HSE06), characterized by flat valence bands predominantly comprised of F-<span><math><mrow><mn>2</mn><mi>p</mi></mrow></math></span> states and narrow conduction bands derived from Tl-<span><math><mrow><mn>6</mn><mi>p</mi></mrow></math></span> orbitals, indicative of a robust ionic insulator. Thermal study demonstrates distinct regimes in heat capacity and entropy, influenced by low-frequency Tl–F vibrations and high-frequency Al–F phonons. The smooth, continuous nature of these curves confirms the absence of phase transitions within the studied temperature range, underscoring the material’s thermodynamic stability. Analysis of optical properties reveals a broad transparency window below 5.92 eV using GGA functional, confirming AlTlF<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>’s potential as a UV-transparent material for protective coatings and optical components. The pronounced anisotropic absorption in the ultraviolet (6-8 eV) and deep-ultraviolet (12-14 eV) regions, particularly the enhanced response for <span><math><mi>y</mi></math></span>/<span><math><mi>z</mi></math></span>-polarized light, suggests specific applicability in polarization-sensitive deep-UV optoelectronics. This directional absorption behavior, combined with the material’s thermal stability, enables the design of specialized photodetectors for extreme environment applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112980"},"PeriodicalIF":2.4,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340415","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":"Cs2KAlY6 (Y = Cl, Br, I): A lead-free double perovskites for optoelectronic and photocatalytic applications","authors":"Attaur Rahman ,&nbsp;Muhammad Haneef ,&nbsp;Bin Amin","doi":"10.1016/j.chemphys.2025.112975","DOIUrl":"10.1016/j.chemphys.2025.112975","url":null,"abstract":"<div><div>This research work investigates the structural, elastic and mechanical, electronic, optical, acoustic, and thermal properties of the cubic, lead-free double perovskites Cs₂KAlCl₆, Cs₂KAlBr₆, and Cs₂KAlI₆. The Full-potential linearized augmented plane wave (FP-LAPW) formulism based on density functional theory (DFT) is employed using WIEN2k simulation code. These perovskites strongly fulfill the Gold-Schmidt tolerance (t_G) and octahedral (μ_o) factor conditions. The negative values of formation enthalpy (<span><math><mo>∆</mo></math></span>H_f) demonstrate their thermodynamic stability. However, the Born’s stability criteria, the elastic and mechanical features, confirms its elastic and mechanical stability. The Cs₂KAlCl₆ and Cs₂KAlBr₆ are ductile, while Cs₂KAlI₆ is brittle, and all the three halide double perovskites exhibit anisotropic behavior, as indicated by their Pugh's &amp; Poisson ratios, Cauchy-pressure and anisotropic factors. The acoustic behaviors of these compounds are explored through sound velocities estimations. Thermal performances are analyzed with Debye &amp; melting temperature, and thermal expansion coefficient. It is evident from the electronic properties, these perovskites are direct band semiconductors having band gap values 4.38, 3.04, and 1.71 eV for Cs₂KAlCl₆, Cs₂KAlBr₆ and Cs₂KAlI₆ respectively. A stepwise tuning of the band gap is observed, driven by the increase in ionic size moving down the halogen group from Cl to Br to I, which gradually reduces the band gap. The threshold values of optical parameters for Cs₂KAlCl₆/(Cs₂KAlBr₆ and Cs₂KAlI₆) start from ultraviolet/(visible light) range and both go on maximum in the ultraviolet region. Hence, offer an open range to be used in optoelectronic and photovoltaic renewable energy applications. Moreover, the alignment of valence and conduction band edge potentials relative to the standard redox potentials of water splitting make these compounds a promising choice for hydrogen production through photocatalysis.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112975"},"PeriodicalIF":2.4,"publicationDate":"2025-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340412","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":"Cooperative and stabilization effects in hydrogen-bonded chains of microhydrated thymine: a QTAIM and TD-DFT study","authors":"Murillo H. Queiroz ,&nbsp;Tiago V. Alves ,&nbsp;Roberto Rivelino","doi":"10.1016/j.chemphys.2025.112976","DOIUrl":"10.1016/j.chemphys.2025.112976","url":null,"abstract":"<div><div>We investigate the thresholds of the cooperative effects in hydrogen-bonded chains formed by thymine with 1 to 6 explicit water molecules. Using Density Functional Theory (DFT), combined with Quantum Theory of Atoms in Molecules (QTAIM) and Time-Dependent DFT (TD-DFT), we analyze the evolution of the electronic density at H-bond critical points (ρ H-bond) and its influence on the excited states. Our results indicate that the cooperative effect is stronger with the first water molecules, followed by weaker contributions beyond four water molecules. TD-DFT calculations reveal corresponding shifts in electronic transitions, linking H-bond topology with spectral changes. These findings contribute to a quantitative understanding of hydration effects in nucleobases, with implications for DNA stability and photochemistry.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112976"},"PeriodicalIF":2.4,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340413","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 and temperature-dependent Raman spectroscopic study of gabapentin polymorphism and determination of its dominant conformer in human serum","authors":"Monalisha Nayak,&nbsp;Ranjan K. Singh","doi":"10.1016/j.chemphys.2025.112974","DOIUrl":"10.1016/j.chemphys.2025.112974","url":null,"abstract":"<div><div>The clinically important drug gabapentin (GBP) exhibits polymorphism, crystallizing in multiple forms (α, β and γ) that differ in molecular packing and spectroscopic signatures. The α, β and γ polymorphs of GBP have been extensively examined through temperature-dependent Raman spectroscopy and density functional theory (DFT) analysis. Temperature-dependent Raman spectra suggested the polymorphic phase transitions with temperature. The α form is predominant at room temperature. The α → β phase transition is observed at ∼150 °C and β → γ phase transition is observed at∼170 °C. These results imply that GBP possesses many different polymorphs, reflecting many conformational states accessible to the molecule. Surface-enhanced Raman spectroscopy (SERS) measurements of GBP in aqueous medium and human serum enable the direct identification of the β-conformer both upon hydration and within the complex biological matrix.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112974"},"PeriodicalIF":2.4,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320883","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":"Protection of chlorinated hydrocarbon as host-guest complex inside C60 fullerene","authors":"Z. Mongashti,&nbsp;S.M. Azami","doi":"10.1016/j.chemphys.2025.112971","DOIUrl":"10.1016/j.chemphys.2025.112971","url":null,"abstract":"<div><div>Chlorinated hydrocarbons are one of the most widely used compounds in industry, while leading to biological hazards that have attracted the attention of environmental researchers. This research investigates confinement of these compounds in fullerene and its effects on chemical and electronic properties. Various parameters, including bonding, interaction and deformation energies, deformation density, and fullerene ellipticity, were investigated, and results indicated how confinement results in compression of the chlorinated hydrocarbon structure and expansion of fullerene to ellipsoidal form. Energetic analyses revealed that the confinement process is non-spontaneous, endothermic, and species are thermodynamically unstable, where by increasing the number of chlorine substitutions, values <!--> <!-->of these energies also increase.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112971"},"PeriodicalIF":2.4,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340414","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 insights into sulfonamide chain length effects on polyamide-based reverse osmosis membranes","authors":"Yayun Hu ,&nbsp;Hongxia Wang ,&nbsp;Jing Lu,&nbsp;Xin Chen,&nbsp;Kangyu Jia,&nbsp;Dong Wang","doi":"10.1016/j.chemphys.2025.112977","DOIUrl":"10.1016/j.chemphys.2025.112977","url":null,"abstract":"<div><div>Polyamide (PA)-based reverse osmosis (RO) membranes are pivotal in water treatment due to their superior separation performance and cost-effectiveness. Nevertheless, challenges such as membrane fouling and the permeability-selectivity trade-off limit their efficiency. This study employs molecular dynamics simulations and density functional theory to systematically investigate the influence of sulfonamide chain length on the performances of PA-based RO membranes. Three sulfonamide-modified PA membranes (M-AESA(<em>n</em>), <em>n</em> = 2, 4, 6) were constructed to assess morphology, hydrophilicity, water transport dynamics, antifouling behavior, and salt resistance. Results demonstrate that increasing sulfonamide chain length enhances membrane roughness, hydrophilicity, and fractional free volume, correlating with improved water diffusion coefficients and flux. Notably, M-AESA(4) exhibits optimal antifouling capability owing to weakened interfacial interactions with calcium alginate foulants. All modified membranes retain robust salt rejection under simulated conditions. These findings provide molecular-level insights into the design of high-performance PA-based membranes, bridging theoretical predictions with practical membrane optimization strategies.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112977"},"PeriodicalIF":2.4,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320881","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":"A systematic investigation on chalcogen vacancies, doping with transition metals, and their complexes in Janus monolayer WSeTe","authors":"D.M. Hoat ,&nbsp;Nguyen Thi Han ,&nbsp;Chu Viet Ha ,&nbsp;Nguyen Quang Hai ,&nbsp;J. Guerrero-Sanchez","doi":"10.1016/j.chemphys.2025.112972","DOIUrl":"10.1016/j.chemphys.2025.112972","url":null,"abstract":"<div><div>In this work, the impacts of chalcogen vacancies and doping with transition metals (Mn and Fe), as well as their complexes, on the electronic and magnetic properties of Janus monolayer WSeTe are investigated using first-principles calculations. Pristine monolayer has good structural stability and exhibits the direct-gap semiconductor nature with a band gap of 1.34 eV. The band gap reductions of the order of 19.40% and 23.88% are obtained by creating single Se and Te vacancies, respectively. Mn doping induces magnetic semiconductor nature with the in-plane magnetic anisotropy (IMA), while the half-metallicity with perpendicular magnetic anisotropy (PMA) is obtained by Fe doping. Further, the effects of vacancy+impurity complexes are examined. Calculations suggest the enhanced magnetic anisotropy of Mn- and Fe-doped WSeTe monolayer by means of creating additional single vacancies. In all cases, magnetic properties are produced primarily by <span><math><mrow><mn>3</mn><mi>d</mi></mrow></math></span> orbital of Mn and Fe atoms, where smaller contributions from the host W, Se, and Te atoms are also observed. Importantly, the antiparallel spin coupling between Mn/Fe and W-Se-Te atoms is confirmed. In addition, the calculated cohesive energies and <em>ab initio</em> molecular dynamics (AIMD) simulations confirm good structural stability of all the defected/doped WSeTe systems, suggesting their experimental feasibility. Our findings may introduce efficient methods to induce magnetism in Janus monolayer WSeTe with feature-rich electronic natures towards spintronic applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112972"},"PeriodicalIF":2.4,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320920","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":"Dimers involving methane: Strength, range, and nature of the intermolecular interaction and their thermodynamic stability in gas-phase","authors":"Rhuiago Mendes Oliveira ,&nbsp;Cassius Marcellus Costa Carvalho ,&nbsp;João Batista Lopes Martins ,&nbsp;Fernando Pirani ,&nbsp;José Roberto dos Santos Politi ,&nbsp;Ricardo Gargano","doi":"10.1016/j.chemphys.2025.112968","DOIUrl":"10.1016/j.chemphys.2025.112968","url":null,"abstract":"<div><div>This work focuses on an accurate theoretical characterization of the strength, range, and nature of the weak intermolecular interaction that controls the formation of CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> <img>CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>, CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> <img>N<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>, and CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> <img>Ar gaseous dimers. It also provides a reliable valuation of the thermodynamic stability of such three adducts and of their relative distribution of populated intermolecular vibrational levels. The formation of these dimers is driven by the negative components of enthalpy and entropy, indicating that these complexes form nonspontaneously through gas-phase collisions. The results also suggest that the main interaction contribution controlling the stability of these adducts is the dispersion attraction. Furthermore, the formation of the CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> <img>CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> complex, driven by the stronger interaction, exhibits the least positive free energy variation over a wide range of considered temperatures. The obtained information is of relevance since it opens up a range of applications in several areas, including chemistry, materials science, and astrophysics.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112968"},"PeriodicalIF":2.4,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320885","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":"Superhydrophobic ZIF-8-based fibrous membranes for highly effective oil-water separation","authors":"Junjie Zhang,&nbsp;Haixia Chen,&nbsp;Jijun Ding,&nbsp;Yongfeng Qu,&nbsp;Haiwei Fu","doi":"10.1016/j.chemphys.2025.112970","DOIUrl":"10.1016/j.chemphys.2025.112970","url":null,"abstract":"<div><div>The superhydrophobic membranes with low-cost, eco-friendly, and high-performance is a current research focus. In this paper, ZIF-8 particles are synthesized at room temperature and subsequently mixed with graphene oxide with controlled proportions. The resulting composite membrane is fabricated on a fibrous substrate via vacuum filtration. By tailoring the surface microstructure, the wettability of the composite film is effectively modulated. Experimental results demonstrate that the membrane exhibits superhydrophobicity, with a water contact angle of 156° and a separation flux of 31,428.77 L·m⁻²·h⁻¹ for low-viscosity oils. The membrane shows excellent separation efficiency (&gt;99 %) across oils with varying viscosities. Furthermore, the separation performance remains stable, with efficiency above 99 % after 20 cycles and above 98 % after a 30-day long-term test. The combination of facile preparation, environmental friendliness, and outstanding separation performance highlights the potential of this composite membrane for low-cost, high-efficiency oil-water separation applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112970"},"PeriodicalIF":2.4,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320880","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":"Silver nanostructure-decorated electrospun polycaprolactone Fibers as a potential wound dressing material","authors":"Mucahit Enes Atabey ,&nbsp;Nazli Oncer ,&nbsp;Asli Yilmaz ,&nbsp;Yuksel Akinay ,&nbsp;Sinan Egri ,&nbsp;Ozlem Egri ,&nbsp;Mehmet Yilmaz","doi":"10.1016/j.chemphys.2025.112969","DOIUrl":"10.1016/j.chemphys.2025.112969","url":null,"abstract":"<div><div>Medical complications associated with wounds result in significant issues that incur billions of dollars in global costs. Consequently, the development of wound dressing materials that are both cost-effective and efficient is becoming increasingly important. This study introduces the concept of utilizing polydopamine (PDA)-assisted silver nanoparticle (AgNP) decoration on polycaprolactone (PCL) electrospun nanofiber (NF) membranes as a robust wound dressing material. The hydrophobicity of PCL NFs was substantially reduced by the PDA layer, which also improved cell adhesion and exhibited tunable antibacterial activity. This adaptable method enabled the precise regulation of the number density and morphology of decorated AgNPs. The morphology, deposition procedure, and content of the AgNPs partially influenced the ultimate bioactivity of the material. We believe that the NF@PDA@AgNP systems will provide unique benefits as an optimal wound dressing material due to their biodegradability, high antibacterial activity, and minimal cytotoxicity.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112969"},"PeriodicalIF":2.4,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320886","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}