Chemical Physics最新文献

{"title":"Spectral–topological predictors of surface reactivity in palladium and Group-10 metals","authors":"Cesar A. de Mello","doi":"10.1016/j.chemphys.2025.113059","DOIUrl":"10.1016/j.chemphys.2025.113059","url":null,"abstract":"<div><div>Palladium’s Madelung anomaly arises from a spectral phase transition that extinguishes the 5s channel, yielding the [Kr]<!--> <!-->4d¹⁰5s<span><math><msup><mrow></mrow><mrow><mn>0</mn></mrow></msup></math></span> ground state. The transition is set by the sign of an asymptotic operator level, enforcing spectral locking of the s amplitude and giving a sub-Ångström evanescent length (<span><math><mo>&gt;</mo></math></span>99.9% suppression at sub-Å radii). This <span><math><msub><mrow><mi>Z</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span> extinction/survival mechanism organizes Group-10 trends: Ni near the boundary, Pd deep in the extinct phase, and Pt partially reactivated by relativistic softening. Chemically, s-extinction narrows the d manifold, shifts the d-band center toward <span><math><msub><mrow><mi>E</mi></mrow><mrow><mi>F</mi></mrow></msub></math></span>, suppresses isotropic mixing, and rationalizes square-planar preference, d-dominated XPS/EELS screening, and near-vanishing Fermi-contact/Knight terms. Angle-integrated XPS shows null s-weight near threshold, as predicted. The asymptotic level maps alloying, strain, coverage, and support/ligand fields to phase control, enabling testable diagnostics and engineering of orbital extinction/reactivation across Group-10 metals.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113059"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836595","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":"Enhanced supercapacitor performance of copper-doped NiO nanostructures synthesized via hydrothermal method","authors":"Khurshid Ahmad ,&nbsp;Faiz Mahmood ,&nbsp;Dibakar Roy ,&nbsp;Alamgir Khan ,&nbsp;Munir Ahmad ,&nbsp;Subhashree Ray ,&nbsp;Naveen Chandra Talniya ,&nbsp;Gunjan Garg ,&nbsp;Islom Khudayberganov ,&nbsp;Egambergan Madrahimovich Xudaynazarov ,&nbsp;Iqra Sarwar","doi":"10.1016/j.chemphys.2025.113060","DOIUrl":"10.1016/j.chemphys.2025.113060","url":null,"abstract":"<div><div>In this study, a simple and low-cost hydrothermal method was used to create Cu-doped NiO with tunable shape. The inclusion of copper enhanced the material's electrical transport and electrochemical activity, leading to a higher charge-storage capacity and better rate performance. XRD and electron microscopy effectively confirmed Cu²⁺ substitution in the NiO lattice, leading to improved surface texturing, reduced crystallite size, and internal strain. At 5 % Cu doping, lattice distortions produced a unique hierarchical flower-like structure composed of thin, uneven Nano sheets. These structural modifications facilitate enhanced ionic transport pathways and more efficient electron transfer, ultimately elevating the material's electrochemical functionality. Optical characterization via UV–visible spectroscopy demonstrated a reduction in the energy band gap, decreasing from 3.14 eV in pure NiO to 2.50 eV in the 5 % Cu-doped variant, suggesting enhanced photoresponse characteristics. Electrochemical evaluation revealed substantial enhancement in pseudocapacitive behavior: specific capacitance values increased from 212 F g⁻¹ for the undoped material to 377 F g⁻¹ for the 5 % Cu-NiO sample when measured at a scan rate of 10 mV/s. Constant current charge-discharge measurements yielded an even higher capacitance of 394 F g⁻¹ at a current density of 1 A g⁻¹.The optimized electrode configuration achieved an energy density of 45 Wh/kg coupled with a power density of 788 W/kg when operated at 3 A g⁻¹. Long-term cycling stability tests demonstrated that the 5 % Cu-NiO electrode maintained 90 % of its initial capacitance alongside 85 % coulombic efficiency even after 10,000 consecutive charge-discharge cycles, confirming remarkable operational stability. These findings validate that strategic copper incorporation substantially improves the electrochemical characteristics of nickel oxide, establishing its potential for advanced energy storage applications with efficient charge storage mechanisms, minimal capacity fade, and robust long-term performance.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113060"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786519","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":"Optoelectronic properties of all-inorganic pseudo-halide perovskite Cs2Pb(SCN)2Br2: a first-principles study","authors":"Waqar Ahmad ,&nbsp;Atta Ur Rahman ,&nbsp;Iftikhar Ahmad ,&nbsp;Imad Khan","doi":"10.1016/j.chemphys.2025.113052","DOIUrl":"10.1016/j.chemphys.2025.113052","url":null,"abstract":"<div><div>The majority of reported two-dimensional (2D) Ruddlesden-Popper (RP) lead halide perovskites, follow the general formula A_n+1B_nX_3n+1 (where <em>n</em> = 1, 2, …), featuring layered perovskite structures interleaved with A-site-substituted organic or inorganic spacer cations. However, X-site-substituted RP halide perovskites (pseudo-halide) remain relatively underexplored. In this work, we performed first-principles investigations of an all-inorganic pseudo-halide 2D perovskite, Cs₂Pb(SCN)₂Br₂, using density functional theory (DFT). The 3D lattice is composed of 2D perovskite layers that function as quantum wells for charge carriers and the spacer layers serve as potential barriers. The calculations for the electronic structures have confirmed that Cs₂Pb(SCN)₂Br₂ holds a direct band gap of 2.69 eV, a low binding energy of 166 meV and a small interlayer distance of 1.69 Å with effective light absorption in the visible spectra. The results from optical characterization signify its promising features for the optoelectronic applications, such as solar cells and light emitting diodes (LEDs). For the evaluation of photovoltaic performance, FTO/SnO₂/Cs₂Pb(SCN)₂Br₂/Cu₂O/Au device structure was simulated, in which SnO₂ serves as electron transport layer (ETL) and Cu₂O as the hole transport layer (HTL). The device in optimized state showed fill factor (FF) of 82.2 %, open-circuit voltage (V_oc) of 1.73 V, power conversion efficiency (PCE) of 19.03 %, and short-circuit density (J_sc) of 13.2 mA cm⁻². The results of this study provides a strong basis for future research focusing on inorganic pseudo-halide perovskites, thus enabling for the development of enhanced photovoltaic performance via experimental and theoretical advancements.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113052"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786520","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":"The nuclear quadrupole moment of barium from the molecular method","authors":"Roberto Luiz Andrade Haiduke","doi":"10.1016/j.chemphys.2025.113055","DOIUrl":"10.1016/j.chemphys.2025.113055","url":null,"abstract":"<div><div>The molecular method is used to determine the nuclear quadrupole moments (NQMs) of two barium isotopes, ¹³⁵Ba and ¹³⁷Ba. Hence, accurate relativistic electric field gradient (EFG) calculations based on the four-component formalism done at the barium nucleus in two diatomic systems, BaO and BaF, are combined with experimental data of nuclear quadrupole coupling constants. The best EFGs are provided by accounting for electron correlation effects from Dirac-Coulomb Coupled Cluster calculations with iterative single and double excitations plus perturbative triples, with additive Gaunt, vibrational, and extra basis set corrections. Therefore, the recommended NQMs for ¹³⁵Ba and ¹³⁷Ba are 155(5) and 239(7) mbarn, respectively.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113055"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733041","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 multifaceted properties of Cs2LiBiX6 (X = F, Br) perovskites for next generation optoelectronic devices","authors":"Md. Minhajul Abedin Nannu ,&nbsp;Md. Sharif Uddin ,&nbsp;Md. Rubayed Hasan Pramanik ,&nbsp;Abdullah Marzouq Alharbi ,&nbsp;Nacer Badi ,&nbsp;Aijaz Rasool Chaudhry ,&nbsp;Ahmad Irfan ,&nbsp;Md. Ferdous Rahman","doi":"10.1016/j.chemphys.2025.113051","DOIUrl":"10.1016/j.chemphys.2025.113051","url":null,"abstract":"<div><div>Growing interest in sustainable, lead-free materials has driven extensive research into alternative compounds for advanced optoelectronic applications such as solar cells and sensors. This study employs first-principles density functional theory (DFT) to explore the structural, electronic, mechanical, and optical properties of Cs₂LiBiX₆ (X = F, Br) double perovskites. Both compounds are found to crystallize in a stable cubic phase, with Cs₂LiBiF₆ exhibiting slightly greater lattice stability. Electronic analysis reveals that both are indirect semiconductors Cs₂LiBiF₆ has a wider bandgap of 4.898 eV, while Cs₂LiBiBr₆ features a narrower 2.917 eV gap due to stronger orbital hybridization in the bromide compound. Mechanical results confirm elastic stability, with Cs₂LiBiF₆ showing moderate stiffness and ductility, while Cs₂LiBiBr₆ displays nearly isotropic behavior. Optical studies demonstrate strong ultraviolet absorption and tunable dielectric responses, highlighting their potential in UV and optoelectronic technologies. Thus, Cs₂LiBiX₆ materials emerge as promising, environmentally friendly candidates for efficient, lead-free optoelectronic devices.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113051"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786516","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":"Temporal evolution characteristics of carbon product in β-HMX thermal decomposition: A theoretical study based on ReaxFF-MD simulations","authors":"Yu Zhang,&nbsp;Zheng-Hua He,&nbsp;Guang-Fu Ji","doi":"10.1016/j.chemphys.2025.113065","DOIUrl":"10.1016/j.chemphys.2025.113065","url":null,"abstract":"<div><div>The dynamic evolution process of carbon products critically influences the reaction behaviors of energetic materials, but is not well understood yet. Here, we employ long-timescale reactive molecular dynamics simulations to investigate the carbon clusters involved in thermal decomposition of β-HMX. The microscopic structure evolution of carbon products and the concurrent heteroatom releases are systematically investigated under varying conditions. Elevated temperature promotes the generation of N₂, H₂O, and CO₂ (at 1 GPa), while high pressure suppresses CO₂ formation and facilitates carbon aggregation. The oxygen migration is identified as the principal driver for carbon cluster evolution, promoting the formation of sp²-hybridized hexagonal frameworks at high temperatures and pressures, ultimately yielding graphene-like or partially amorphous carbon phases. The five-membered rings play an important role on carbon structure evolution, by coupling with seven- or eight-membered rings and promoting their conversion into more stable six-membered rings.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113065"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786512","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 rare case of solid state tautomerism of 2-carbamido-1,3-indandione: Very fast intramolecular proton transfer","authors":"Venelin Enchev ,&nbsp;Marin Rogojerov ,&nbsp;Tsvetan Zahariev ,&nbsp;Nina Stoyanova ,&nbsp;Sofiya Ivanovska ,&nbsp;Atanas Kurutos ,&nbsp;Ivelina Georgieva","doi":"10.1016/j.chemphys.2025.113073","DOIUrl":"10.1016/j.chemphys.2025.113073","url":null,"abstract":"<div><div>Solid-state tautomerism of 2-carbamido-1,3-indandione (CAID) was examined by periodic density functional calculations and infrared spectroscopy. Crystal structure models of <strong>A</strong> and <strong>B</strong> tautomers, consisting of four molecules in the unit cell, were used to simulate the intermolecular interactions in the solid state. The tautomer dynamic equilibrium in time (20 ps) at different temperatures was theoretically evaluated by first principle molecular dynamics (MD). The rare phenomenon in solid state was identified, which is expressed in the coexistence of two tautomers, the equilibrium of which varies with temperature due to simultaneous conversion via intramolecular proton transfer. MD calculations predicted a dominant presence of <strong>A</strong>, and an increase in the amount of B (3–6 %) at higher temperatures. It was shown that the coexistence of tautomers is evident in the experimental IR and UV–Vis spectra of CAID.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113073"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880063","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":"Photodissociation and proton transfer dynamics in thymine cluster cations: A TOF mass spectrometry and ADMP simulation study","authors":"Md. Alauddin ,&nbsp;Seung Min Park","doi":"10.1016/j.chemphys.2025.112994","DOIUrl":"10.1016/j.chemphys.2025.112994","url":null,"abstract":"<div><div>This research examines the photodissociation dynamics of thymine cluster cations (dimers to tetramers) under various laser wavelengths using TOF mass spectrometry and computational simulations. Protonated thymine (TH⁺) emerges as the primary fragment, driven by intradimer proton transfer (IPT) in the excited neutral or ionic states. Fragmentation pathways vary with cluster size and excitation energy, with larger clusters showing lower intensity in dissociation. Computational results confirm IPT as a stabilizing mechanism in dimers. Atom-centered Density Matrix Propagation (ADMP) simulations reveal that hydrogen bonds remain stable up to 400 fs, with IPT and structural fluctuations occurring within the first 200 fs, indicating rapid intracluster dynamics.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 112994"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681705","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-MD simulations of the oxidation mechanism of pentacyclotetradecane","authors":"Chong-Chong She ,&nbsp;Tian-Cheng Zhang ,&nbsp;Li-Xiao-Song Du ,&nbsp;Peng Wang ,&nbsp;Tao Fang ,&nbsp;Xiao Ma ,&nbsp;Liang Song","doi":"10.1016/j.chemphys.2025.113031","DOIUrl":"10.1016/j.chemphys.2025.113031","url":null,"abstract":"<div><div>The molecular structure of linear polycyclic hydrocarbon makes pentacyclotetradecane (C₁₄H₂₀) a candidate for high energy density fuel, with potential applications as a hydrocarbon fuel for aircraft. Results show that the combustion of C₁₄H₂₀ requires activation energies ranging from 93.14 to 123.37 kJ/mol. The main pathway for the initial decomposition of C₁₄H₂₀ involves the cleavage of C<img>C and C<img>H bonds. A significant amount of C₁₄H₂₀ is consumed by the reaction of C₁₄H₂₀ → 2 C₇H₁₀, where the C<img>C bond connecting the two ring compounds is broken and the same ring structure C₇H₁₀ is formed. O₂, OH, and HO₂ contribute significantly to the consumption of C₁₄H₂₀ via pathways such as C₁₄H₂₀ + M → C₁₄H₁₉ + M-H (M = O₂, OH, HO₂). The ring-opening reactions of C₁₄H₂₀ mainly occur in six-membered rings rather than five-membered rings. Additionally, the consumption and formation pathways of main products such as C₂H₄, C₂H₂, and CH₂O are detailed.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113031"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145616142","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 effect of strain engineering on the structure and properties of energetic silver-based perovskite","authors":"Feng Gu,&nbsp;Jijun Xiao","doi":"10.1016/j.chemphys.2025.113056","DOIUrl":"10.1016/j.chemphys.2025.113056","url":null,"abstract":"<div><div>Organic-inorganic energetic perovskite materials have become a major attraction in the field of energetic materials. Silver-based energetic perovskite (H₂pz)[Ag(ClO₄)₃] (PAP-5) has garnered significant interest due to its unique detonation properties, mechanical, electrical, and structural characteristics. Since strain engineering serves as a powerful tool for modifying the physical properties and crystal structure of perovskite materials, this study employs density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations to investigate the microstructural characteristics of PAP-5 under mechanical loading. The focus includes its structural evolution, band gap, electron charge density, mechanical stability, and interatomic/molecular interactions within the material. It is found that the compressive strength of PAP-5 is greater than the tensile strength, and the stress in different directions is anisotropic. The analysis of bond length and bond angle show that tensile strain has a greater influence on the structure of PAP-5. The band gap will shrink under tensile strain and fluctuate under compressive strain, which is explained from the total density of states. PAP-5 exhibits elastic anisotropy after strain is applied, showing brittleness and ductility during tension and compression respectively. The results of Hirshfeld surface analysis show that the structure of BX₃ is more responsive to the applied strain than that of A-site cation.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113056"},"PeriodicalIF":2.4,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733042","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}