Chemical Physics最新文献

{"title":"Thermodynamics of free radical scavenging activity of deprotonated hibiscetin towards reactive oxygen and nitrogen species","authors":"C. Ragi,&nbsp;P.C. Sumayya,&nbsp;K. Muraleedharan","doi":"10.1016/j.chemphys.2025.112768","DOIUrl":"10.1016/j.chemphys.2025.112768","url":null,"abstract":"<div><div>Deprotonated flavonoids are known to be more potent antioxidants than neutral forms. This study examined the reaction enthalpies for the mono-deprotonated forms of the most hydroxylated flavonol, hibiscetin, concerning hydrogen atom transfer (HAT) and sequential proton-loss electron-transfer (SPLET) mechanisms. Since deprotonation is highly prevalent in the aqueous medium, it was chosen as the medium of investigation. Deprotonated hibiscetin prefers to enter the SPLET reaction pathway to HAT or electron transfer. Hence, the sequential double proton loss electron transfer (SdPLET) route offers a stronger justification for the antioxidant activity of hibiscetin in the aqueous phase. The sequential proton loss hydrogen atom transfer (SPLHAT) process can also take place in the aqueous media competitively. The viability of Hibiscetin and mono-deprotonated Hibiscetin in scavenging five reactive oxygen and nitrogen species (ROS and RNS) that are known to damage biological systems in the aqueous solution was assessed by calculating the equilibrium constant and redox potential of electron transfer. The hydroxyl radical exhibited the strongest attraction for the hydrogen atom and electron among the ROS and RNS under consideration. Its equilibrium constants also indicated that hibiscetin and deprotonated hibiscetin scavenge it in a highly advantageous and spontaneous manner. The higher values of the equilibrium constant in the case of mono-deprotonated hibiscetin confirmed its better capacity for scavenging reactive species.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112768"},"PeriodicalIF":2.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144107091","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 calculations study:The tunability and optical properties of the ZrS2/CdSe heterojunction","authors":"Dan Li ,&nbsp;Xing Wei ,&nbsp;Wentao Luo ,&nbsp;Yan Zhang ,&nbsp;Yun Yang ,&nbsp;Jian Liu ,&nbsp;Ye Tian ,&nbsp;Li Duan","doi":"10.1016/j.chemphys.2025.112758","DOIUrl":"10.1016/j.chemphys.2025.112758","url":null,"abstract":"<div><div>This research employed first-principles calculations to investigate the geometric, electronic, and optical properties of the ZrS₂/CdSe heterojunction. The most stable configuration is achieved at an interlayer spacing of 3.29 Å (T1), featuring a direct bandgap of 0.85 eV, smaller than the individual monolayers, and forming a Type-II band alignment. Under an applied electric field, the band alignment transitions from Type-II to Type-I. Additionally, biaxial strain ranging from −10 % to 8 % induces a semiconductor-to-metal transition, showcasing its potential in photodetection and light-emitting diodes. The heterojunction demonstrates stronger ultraviolet absorption compared to the monolayers, with absorption properties effectively modulated by electric fields and strain. These tunable electronic and optical characteristics make the ZrS₂/CdSe heterojunction a promising candidate for advanced optoelectronic technologies.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112758"},"PeriodicalIF":2.0,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144083664","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":"Improved electrocatalytic performance of NdCoO3/rGO for oxygen evolution reaction","authors":"Zeinhom M. El-Bahy ,&nbsp;Taghrid S. Alomar ,&nbsp;Najla AlMasoud ,&nbsp;Muhammad Abdullah ,&nbsp;Tehreem Zahra ,&nbsp;Amal A. Al-wallan ,&nbsp;Hafiz Muhammad Tahir Farid","doi":"10.1016/j.chemphys.2025.112774","DOIUrl":"10.1016/j.chemphys.2025.112774","url":null,"abstract":"<div><div>An important concern in present research is the enhancement of an electrochemical water oxidation mechanism that can produce clean energy in a more cost-effective, efficient and reliable manner. A key aspect of this study is the generation of electrocatalysts that are both affordable and long-lasting. Cost-effective metal oxides are more advantageous than other media for the oxygen evolution reaction (OER) in basic electrolytes. Due to their impressive electrical properties and the potential for enhanced performance, perovskite-based composites have become highly valuable for the water oxidation reaction. In this report, we described the synthesis of rGO@NdCoO₃ using a sonication process employed toward the OER process. Furthermore, the rGO@NdCoO₃ composite demonstrated a very favorable overpotential (η) of 216 mV at current density (C_d) of 10 mA/cm² and decreased Tafel slope (39 mV/dec). It remains durable for 35 h and even after going through 2000^th cycles. The composite of rGO@NdCoO₃ demonstrated various advantageous effects, such as decreased overpotential, enhanced catalytic C_d, improved charge transfer kinetics and increased ECSA value of 581.25 cm². Based on the research, it is evident that the fabricated material demonstrated exceptional efficiency and durability as an electrocatalyst in energy conversion systems.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"596 ","pages":"Article 112774"},"PeriodicalIF":2.0,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144069432","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":"Computational prediction of sublimation enthalpy of organic compounds using the Monte Carlo technique","authors":"Zahrah Makari ,&nbsp;Fereshteh Shiri ,&nbsp;Shahin Ahmadi","doi":"10.1016/j.chemphys.2025.112767","DOIUrl":"10.1016/j.chemphys.2025.112767","url":null,"abstract":"<div><div>Sublimation enthalpy is a key property of organic compounds, influenced by intermolecular interactions and challenging to predict for new compounds lacking known crystal structures. This study developed a QSPR model to reliably estimate sublimation enthalpy in organic compounds using advanced molecular modeling techniques and Monte Carlo-based optimization. Trained on 1300 compounds, the model achieved high predictive accuracy (R²_train = 0.98, R²_val = 0.99 and RMSE_(train) = 2.88 KJ/mol, RMSE_(val) = 5.2306 KJ/mol for split 7). Mechanistic insights revealed that certain structural features such as double bonds and specific atoms increase sublimation enthalpy. These findings provide valuable guidance for designing organic compounds with desirable properties.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"596 ","pages":"Article 112767"},"PeriodicalIF":2.0,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143948747","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":"Magnetic properties of transition elements adsorbed B2S2 monolayers","authors":"Wenxu Zhao ,&nbsp;Bin Xu ,&nbsp;Cheng Qian ,&nbsp;Mengran Yang ,&nbsp;Dan Zhou ,&nbsp;Yusheng Wang ,&nbsp;Zan Cao ,&nbsp;Lin Yi","doi":"10.1016/j.chemphys.2025.112769","DOIUrl":"10.1016/j.chemphys.2025.112769","url":null,"abstract":"<div><div>The purpose of this work is to investigate how different transition elements can affect the magnetic properties of B₂S₂ monolayers. The present work will help to reveal the microscopic mechanisms of the interaction of transition elements with B₂S₂ monolayers. The electronic properties and magnetic properties of materials with different transition element atoms (Co, Cr, Fe, Mn, Ti, V, Cu, Ni and Zn) adsorbed on a monolayer of B₂S₂ substrate have been calculated based on the first nature principle. We found that different atoms adsorbed produce different magnetic moments, the total magnetic moment ranges from 0 to 4.00 μB, among which Cr-B₂S₂ produces the largest magnetic moment of 4.00 μB. The energy band gaps of the different adsorption systems are also different, with the minimum reaching 0.0039 eV and the maximum 1.90 eV. Valence electron orbital hybridization occurs between the transition element atoms and the atoms on the neighboring substrates. After calculation, we found that the Tm atoms are charge donors and the monolayer B₂S₂ is charge acceptors, and the charge transfer generally occurs between the Tm atoms and their neighboring S atoms, and the overall Tm-B₂S₂ system is n-type doped. The results are calculated to show that all atoms except Zn atoms are stably adsorbed in monolayer B₂S₂, and our study can demonstrate that the system of transition element atoms (Tm) adsorbed in monolayer B₂S₂ has potential applications in spintronics and magnetic memory.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"596 ","pages":"Article 112769"},"PeriodicalIF":2.0,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143936963","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":"Modeling the effects of thermal fluctuations on proton tunneling kinetics in systems with intermolecular hydrogen bonding","authors":"Luca Nanni","doi":"10.1016/j.chemphys.2025.112771","DOIUrl":"10.1016/j.chemphys.2025.112771","url":null,"abstract":"<div><div>The environmental temperature plays an important role in the kinetics of proton tunneling in biological systems, where molecules are bound through intermolecular hydrogen bonds. Developing a quantum mechanical model that can accurately predict the rate and mechanism of hydrogen transfer is challenging. This study proposes a model in which the donor group is treated using the semiclassical approximation, while the hydrogen bonds, whose geometry is influenced by thermal fluctuations, are modeled as classical springs. This approach allows for a straightforward calculation of how the rates of proton tunneling and the kinetic isotope effects vary with temperature. The model is tested using the formic acid dimer to assess its predictive capability.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112771"},"PeriodicalIF":2.0,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144070292","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 thermodynamic stability and electronic structure of ZnNb₂O₆(001) surface through first-principles calculations","authors":"Anqi Yang ,&nbsp;Qian Chen ,&nbsp;Lilong Zhang ,&nbsp;Yao Zhu ,&nbsp;Quan Xie","doi":"10.1016/j.chemphys.2025.112765","DOIUrl":"10.1016/j.chemphys.2025.112765","url":null,"abstract":"<div><div>The polar surface of ZnNb₂O₆ material holds considerable importance and practical significance. Using first-principles calculations, the structure, charge redistribution, electronic properties, and thermodynamic stability of the ZnNb₂O₆(001) surface were examined. The crystal was cleaved along the (001) plane to form nine surface slab models, of which five surface terminations are feasible under specific chemical conditions. The optimized structural configurations of these terminations illustrate the charge transfer due to polarity compensation and the differences in electronic structure caused by surface reconstruction. Surface metallization, resulting from the atypical saturation of surface states, acts as a compensatory mechanism for pronounced surface polarity. The ZnNb₂O₆(001) surface slab exhibits a shift in its electronic band structure, transitioning from semiconductor characteristics to metallic properties. The nature of the charge carriers (p-type or n-type) depends on the specific surface termination. The unique electronic properties of the ZnNb₂O₆(001) surface arise from significant variations in volume and polarity compensation. This detailed atomic-level understanding is expected to stimulate further theoretical and experimental investigations into this novel photocatalytic material.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112765"},"PeriodicalIF":2.0,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144089901","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":"Effect of sulfur doping on the electronic structures, optical and photocatalytic properties of KTaO3 perovskites: DFT calculations","authors":"Z. Ech-charqy ,&nbsp;A. El Badraoui ,&nbsp;A. Elkhou ,&nbsp;M. Ziati ,&nbsp;H. Ez-Zahraouy","doi":"10.1016/j.chemphys.2025.112759","DOIUrl":"10.1016/j.chemphys.2025.112759","url":null,"abstract":"<div><div>Perovskite oxides such as KTaO₃ have attracted a great deal of scientific interest in recent years thanks to their remarkable properties, which enable them to be used in a variety of fields. In our case, we've focused on photovoltaic and photocatalytic applications, and it's well-known that these techniques are based on the use of semiconductors with a specific gap value, which indicates that the gap value is an important element that influences the efficiency of panels. The objective of this study is to decrease the gap value by applying the KTaO_3-xS_x doping process with different percentages of S (x = 0 %, 4.16 %, 8.32 %, and 12.5 %) to determine the electronic, optical, and photocatalytic properties of the different percentages of S using density functional theory (DFT). As a result, we reduced the gap value from 3.86 eV to 1.24 eV corresponding to 0 % S and 12.5 % S respectively, and the bandgap changed from an indirect bandgap equivalent to 0 % S to a direct bandgap for 4 %, 8 % and 12 % S.</div><div>Conduction and valence band edges were also determined in relation to the oxidation and reduction potentials of water. These results indicate that S-doped KTO_3-xS_x (x = 4.16 % to 8.32 %) are potential candidates for hydrogen production. However, under pH conditions, only KTO_3-xS_x compounds (x = 0 % and 4.16 %) can be used for hydrogen production by photocatalysis of water using solar radiation.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"596 ","pages":"Article 112759"},"PeriodicalIF":2.0,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143942281","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":"Insight into spin polarization, Fermi surface, band structure and Thermophysical properties of Sc2ZrSi inverse Heusler","authors":"Saleem Yousuf ,&nbsp;Khalid Bin Masood ,&nbsp;Shahzad Iqbal ,&nbsp;Abdulaziz Abdullah Alsahli ,&nbsp;Masroor Ahmad Bhat ,&nbsp;Arshid Mir","doi":"10.1016/j.chemphys.2025.112749","DOIUrl":"10.1016/j.chemphys.2025.112749","url":null,"abstract":"<div><div>The origin of half-metallicity, spin behavior, thermoelectrics and thermodynamics of inverse full-Heusler Sc₂ZrSi alloy are explored using the density functional theory (DFT). The calculation of ground state energy, confirm the XA-type structure with Hg₂CuTi-prototype structure with F-43 m space group symmetries. Band structure and occupation of density of states at the Fermi level convey the semiconducting nature with an indirect band gap of 0.52 eV. Semi-classical Boltzmann transport theory is used to determine various thermoelectric coefficients to infer about its capability as waste heat recovery system. The Seebeck coefficient and electrical conductivity measurements also convey semiconducting band structure over all chemical potentials. The thermoelectric efficiency measured through zT calculation with a value of 0.5 at 1200 K, convey the material can be used as high temperature thermoelectric material. The thermodynamics using Debye temperature, specific heat and thermal expansion coefficient define low anharmonicity and low lattice thermal conductivity of the material. The overall thermophysical assets suggest the material has a potential stand for spintronic and thermoelectric applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"596 ","pages":"Article 112749"},"PeriodicalIF":2.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143895213","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":"Extrusion of carbon with SON in heterocycles for enhanced static and dynamic hyperpolarizabilities and light harvesting efficiencies","authors":"Farah Tayyaba Khan ,&nbsp;Muhammad Ibrahim ,&nbsp;Afifa Yousuf ,&nbsp;Muhammad Arif Ali","doi":"10.1016/j.chemphys.2025.112761","DOIUrl":"10.1016/j.chemphys.2025.112761","url":null,"abstract":"<div><div>The current study investigates the electronic, spectroscopic, and nonlinear optical (NLO) properties of cyclic pyrrole/furan/thiophene (CPFT) compounds and their derivatives using density functional theory (DFT) calculations. The electronic and absorption characteristics were analyzed using four methods—B3LYP-D3, M06-2×, CAM-B3LYP, and ωB97XD—with the 6-311G (d, p) basis set. Molecular geometries were optimized, and frontier molecular orbital (FMO) analysis was performed to understand structure-property relationships. Compound 1d exhibited the smallest HOMO-LUMO gap (3.79 eV) and the highest NLO response due to the presence of an electron-donating -NH₂ group. Molecular electrostatic potential (MEP) analysis identified electron-rich (nucleophilic) and electron-deficient (electrophilic) regions within the molecules. The introduction of reducing and oxidizing agents significantly influenced the total NLO polarizability. Dipole moment (μ), linear polarizability (<em>α</em>_₀), static and dynamic second-order NLO polarizability (<em>β</em>) and light harvesting efficiencies were calculated for all compounds. 1d displayed the largest static second-order NLO response (12,846 a.u.), approximately 1252 times greater than other derivatives and higher LHE of 97 %. Electron localization function (ELF-π) and localized orbital locator (LOL-π) analyses confirmed enhanced electron delocalization in the series-1 compounds. Time-dependent DFT (TD-DFT) calculations determined excitation energies, oscillator strengths, and absorption wavelengths. The absorption spectra showed maximum peaks between 423 and 500 nm for series-1 as compared to series-2 and series-3, supporting strong NLO activity. Frequency-dependent hyperpolarizability at longer wavelengths (1460 and 1907 nm) further enhanced NLO responses. Natural bond orbital (NBO) analysis revealed stabilizing hyperconjugative interactions. These findings demonstrate that CPFT derivatives are promising candidates for optoelectronic and NLO applications, providing a foundation for designing advanced functional materials.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"596 ","pages":"Article 112761"},"PeriodicalIF":2.0,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143886258","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}