Chemical Physics最新文献

{"title":"DFT investigation of band gap and conductivity in pristine and doped Polyacetylene oligomers: A new extrapolation approach","authors":"Igor S. Kovalev ,&nbsp;Alexander S. Novikov ,&nbsp;Grigory V. Zyryanov","doi":"10.1016/j.chemphys.2025.113004","DOIUrl":"10.1016/j.chemphys.2025.113004","url":null,"abstract":"<div><div>The electronic properties of polyacetylene (PA) isomers and their doped derivatives were investigated using density functional theory (DFT) at the PM3/B3LYP/def2-TZVP level. By studying a series of oligomers with increasing conjugation length, we determined the asymptotic band gaps to be 1.26 eV for <em>trans</em>-PA and 2.01 eV for <em>cis</em>-PA, rationalizing the higher conductivity of the <em>trans</em>-isomer. A novel nonlinear extrapolation method was developed to accurately predict the band gap of the infinite polymer from a minimal set of oligomer calculations. Furthermore, we demonstrate a dramatic band gap reduction—up to 97 %—upon p-doping via oxidation or bromination, and n-doping via deprotonation or reduction, confirming the transition to a metal-like state. The insulating nature of polytetrafluoroethylene (PTFE) was concurrently verified. Our findings provide a robust computational framework for screening optimal dopants to maximize PA conductivity.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113004"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145425054","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":"Surface self-diffusion of ice under high hydrostatic pressure","authors":"Carlos L. Di Prinzio ,&nbsp;Luis N. Gerez ,&nbsp;Esteban Druetta ,&nbsp;Pastor I. Achával ,&nbsp;Guillermo G. Aguirre Varela","doi":"10.1016/j.chemphys.2025.113025","DOIUrl":"10.1016/j.chemphys.2025.113025","url":null,"abstract":"<div><div>The temporal evolution of the width of a scratch on the basal plane (0001) of a pure ice single crystal was analyzed under hydrostatic pressures of 0.1 <em>MPa</em> and 10 <em>MPa</em>. The sample was immersed in ultrapure silicone oil at −5 <em>°C</em> to suppress sublimation. A custom-designed pressurized cell enabled the application of controlled hydrostatic pressure, while time-lapse imaging was conducted using an optical microscope equipped with a digital camera. Images of the scratch were acquired at 30-min intervals over a 24-h period. Quantitative analysis of the scratch profiles was performed using image processing software, allowing for the extraction of the time-dependent broadening of the scratch under the specified hydrostatic pressures. From this, the surface self-diffusion coefficient was determined, providing insight into pressure-dependent surface mass transport mechanisms in ice.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113025"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576689","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":"Nonadiabatic dynamics study of the Sr+(4d2D) + H2(v = 0, 1; j = 0) reaction","authors":"Xiujuan Zhang,&nbsp;Wentao Li","doi":"10.1016/j.chemphys.2025.112995","DOIUrl":"10.1016/j.chemphys.2025.112995","url":null,"abstract":"<div><div>Dynamics studies were performed on the Sr⁺(4d²D) + H₂(<em>v</em> = 0, 1; <em>j</em> = 0) reaction based on diabatic potential energy surfaces. The results demonstrate that the reaction pathway Sr⁺(4d²D) + H₂ is the primary mechanism for SrH⁺ formation, exhibiting significantly higher reactivity compared to the Sr⁺(5s²S) + H₂ reaction. Calculated dynamical properties including reaction probabilities, integral cross sections, and differential cross sections for SrH⁺ formation, reveal that vibrational excitation of the H₂ reactant substantially enhances reactivity. Furthermore, the differential cross sections are predominantly forward-scattered, indicating that the abstraction mechanism dominates the reaction.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112995"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145474613","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":"Dielectric characterization and thermodynamic analysis of iso-propyl acetate and Iso-amyl acetate with dimethyl sulphoxide binary mixtures using time domain reflectometry","authors":"Pallavi D. Hambarde,&nbsp;Nitin P. Garad,&nbsp;Ashok C. Kumbharkhane","doi":"10.1016/j.chemphys.2025.113024","DOIUrl":"10.1016/j.chemphys.2025.113024","url":null,"abstract":"<div><div><ul><li><span>•</span><span><div>Investigated the dielectric properties and molecular interactions of isopropyl acetate (IPAc) and isoamyl acetate (IAA) with dimethyl sulfoxide (DMSO) binary mixtures using Time Domain Reflectometry (TDR) over 10 MHz–30 GHz.</div></span></li><li><span>•</span><span><div>Determined static dielectric constant (ε₀) and relaxation time (τ) by fitting complex permittivity spectra to the Cole–Davidson model with least squares fitting.</div></span></li><li><span>•</span><span><div>Evaluated molecular interactions and dielectric relaxation through Bruggeman factor, Kirkwood correlation factor, excess permittivity, and thermodynamic parameters.</div></span></li><li><span>•</span><span><div>Revealed structural differences and molecular interactions influenced by chain length and concentration, providing insights into dipole orientation and mixture behavior.</div></span></li></ul></div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113024"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145526392","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":"Planar pentacoordinate beryllium in neutral Be©Al5H5 species: Alkaline-earth aromaticity and covalent bonds","authors":"Hong-Lang Yu ,&nbsp;Qiao-Qiao Yan ,&nbsp;Wen-Xing Zhang ,&nbsp;Yu Chen ,&nbsp;Yang-Miao Ou ,&nbsp;En-Dong Huang ,&nbsp;Shao-Jie Li ,&nbsp;Yi-Ran Li","doi":"10.1016/j.chemphys.2025.112984","DOIUrl":"10.1016/j.chemphys.2025.112984","url":null,"abstract":"<div><div>We unveiled an unprecedented Be©Al₅H₅ motif featuring a planar pentacoordinate beryllium atom. This molecule exhibits robust electronic, thermodynamic, and dynamic stability up to 500 K. Our analysis confirmed that Be©Al₅H₅ exhibits σ/π double aromaticity. Both this aromaticity and the five outermost hydrogen atoms were indispensable for maintaining its molecular planarity. We further explored the substitution chemistry of Be©Al₅H₅ by replacing the outer hydrogen atoms with strong electron-withdrawing groups (-COOH). DFT and MP2(full) calculations confirmed that both the mono- and penta-substituted derivatives maintain rigid ppBe structures. The computed solvation free energies showed that the ppBe Be©Al₅H₅, Be©Al₅H₄(COOH) and Be©Al₅(COOH)₅ dissolve more readily in polar solvents. Calculations indicated that these compounds can be readily extracted from benzene or cyclohexane into the aqueous phase. Given its unique solubility in polar solvents and a strong potential for generating derivatives, we suggest that Be©Al₅H₅ could serve as a promising building block for aluminum‑beryllium covalent compounds.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112984"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145425055","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":"Biosorption of Lead (II) and cadmium (II) ions from aqueous solution by buckwheat (Fagopyrum Esculentum) hulls biosorbent: kinetic, equilibrium and thermodynamic studies","authors":"Tayyab Tahir ,&nbsp;Rūta Druteikienė ,&nbsp;Zita Žukauskaitė ,&nbsp;Jūratė Vaičiūnienė ,&nbsp;Aušra Selskienė ,&nbsp;Ilja Ignatjev ,&nbsp;Muhammad Adnan","doi":"10.1016/j.chemphys.2025.112997","DOIUrl":"10.1016/j.chemphys.2025.112997","url":null,"abstract":"<div><div>In this study buckwheat hull was used as an efficient, cheap and environmentally safe for the removal of Pb(II) and Cd(II) from an aqueous solution through optimizing various experimental parameters such as temperature (25–50 °C), solution pH (2–6 for Pb(II) and 2–7 for Cd(II)), amount of buckwheat hulls (0.1–0.35 g), initial Pb(II) and Cd(II) concentration (5–400 mg L⁻¹) and contact time (30–1440 min). SEM, FTIR, EDX, and pH_pzc measurements were used to analyze buckwheat hulls before and after biosorption. Kinetic data fitted best to the pseudo-second-order model due to higher values of R² (R²_Pb(II) = 0.999 and R²_Cd(II) = 0.999). Equilibrium data matched the Langmuir model, yielding sorption capacities of 87.72 mg·g⁻¹ for Pb(II) and 23.2 mg·g⁻¹ for Cd(II), indicating monolayer adsorption. Analysis of thermodynamic parameters, revealed the non-spontaneous and exothermic characteristics of the removal of Pb(II) and Cd(II) by buckwheat hulls.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112997"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145425059","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":"Micro-Raman study of H(l) precursor states of ultra-dense hydrogen H(0)","authors":"Leif Holmlid ,&nbsp;Linnéa Gunnarsson","doi":"10.1016/j.chemphys.2025.113017","DOIUrl":"10.1016/j.chemphys.2025.113017","url":null,"abstract":"<div><div>We show that micro-Raman spectroscopy is useful for studying hydrogen Rydberg Matter of the type H(<em>l</em>) at the generating catalyst surface. The excited hydrogen atoms comprising the H(RM) materials are observed in the anti-Stokes range, in the same way as the excited potassium atoms in potassium Rydberg Matter K(RM) were previously observed (Alpermann and Holmlid 2007). Atomic hydrogen transitions are observed at 320 K. This gives strong evidence for the formation of Rydberg Matter of atomic hydrogen on the potassium containing catalyst. Adsorbed hydrogen H₂ molecules and other hydrogen containing molecules are observed in the Stokes range at shifts up to 4239 cm⁻¹.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113017"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576681","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":"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":"2026-03-01","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":"Exploring the differences in thermal decomposition mechanisms between crystalline and nanoscale 3-nitro-1,2,4-triazole-5-one by molecular dynamics simulations","authors":"Jincheng Ji ,&nbsp;Simin Zhu ,&nbsp;Changxin Li ,&nbsp;Weihua Zhu","doi":"10.1016/j.chemphys.2025.113014","DOIUrl":"10.1016/j.chemphys.2025.113014","url":null,"abstract":"<div><div>Density-functional tight-binding molecular dynamics simulations (DFTB-MD) were used to simulate the thermal decomposition of crystalline and nanoscale 3-nitro-1,2,4-triazole-5-one (NTO) at different temperatures. The results of MD simulations indicate that the initial decomposition mechanism of both crystalline and nanoscale NTO are dominated by the single molecule decomposition. In crystalline NTO, the rearrangement of -NO₂ and direct ring opening are the dominant decomposition pathways. The C-NO₂ homolysis is the main decomposition path for nanoscale NTO, and the decomposition mechanism of nanoscale NTO is significantly influenced by temperature. The activation energy for the decomposition of crystalline NTO is 15.59 kcal·mol⁻¹, which is higher than that of 9.81 kcal·mol⁻¹ for nanoscale NTO, indicating that the activation energy for the decomposition of nanoscale explosives is lower than that of crystalline explosives in this work. This study could provide theoretical guidance for understanding of the thermal reactions of explosives in different aggregation states.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113014"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145474918","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":"Urchin-like cl-doped NiCo bimetallic fluorides for high-performance asymmetric supercapacitors","authors":"Feng Guo ,&nbsp;BianTao Wu ,&nbsp;YanXin Yang ,&nbsp;ZhangSheng Liu ,&nbsp;PeiZhong Feng","doi":"10.1016/j.chemphys.2025.113002","DOIUrl":"10.1016/j.chemphys.2025.113002","url":null,"abstract":"<div><div>Cl-doped NiCo bimetallic fluorides are fabricated via a solvothermal process and subsequent fluoridization. During the fluoridization, the flower-like precursor NiCo-Cl layered double hydroxide (LDH) tends to be transformed into urchin-like morphology. As-obtained (Ni,Co)(F_1-xCl_x)₂ samples (NCFC-x, x = 0, 10, 15, 20 and 25) exhibit excellent electrochemical performance, among which NCFC-20 provides the highest specific capacitance of 2569 F g⁻¹ at a current density of 2 A g⁻¹ and remarkable cycling stability of 79.0 % capacity retention after 7000 cycles. Correspondingly, the assembled NCFC-20//active carbon asymmetric supercapacitor delivers a high energy density (37.3 Wh kg⁻¹) at a power density of 850 W kg⁻¹ and outstanding cycling stability of 88.7 % capacity retention after 6000 cycles. The superior electrochemical performance of NCFC-20 can be attributed to the synergistic effect of typical urchin-like structure and Cl ion doping. Such a material shows an enormous potential for applications in high-performance supercapacitor.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113002"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145425050","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}