Transforming CO2 into valuable C1 products or fuels with renewable energy is a key approach for tackling the dual challenges of climate change and the energy crisis. A highly efficient catalyst for the CO2 reduction reaction (CO2RR) to C1 products (CO, HCHO, CH3OH, CH4) is constructed by anchoring TM3 (TM = Sc-Zn) transition metal clusters on the edge or surface of BN. This study, density functional theory (DFT) calculations are employed to investigate the reaction mechanism of CO2 reduction on these catalysts. The results suggest that the limiting potentials for CO generation on s-Ni3@BN and e-Ni3@BN are as low as −0.13 V and −0.21 V, respectively. Moreover, e-Co3@BN is a highly efficient electrocatalyst for C1 product formation, with limiting potentials for producing CO, HCHO, CH3OH, and CH4 of −0.35 V, −0.46 V, −0.46 V, and −0.46 V, respectively
{"title":"Electrochemical CO2 reduction over BN-supported transition metal trimers: a DFT study","authors":"Haiyue Liao , Jia Peng , Jieyao Ruan , Xin Lian , Wenlong Guo","doi":"10.1016/j.chemphys.2026.113091","DOIUrl":"10.1016/j.chemphys.2026.113091","url":null,"abstract":"<div><div>Transforming CO<sub>2</sub> into valuable C1 products or fuels with renewable energy is a key approach for tackling the dual challenges of climate change and the energy crisis. A highly efficient catalyst for the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) to C1 products (CO, HCHO, CH<sub>3</sub>OH, CH<sub>4</sub>) is constructed by anchoring TM<sub>3</sub> (TM = Sc-Zn) transition metal clusters on the edge or surface of BN. This study, density functional theory (DFT) calculations are employed to investigate the reaction mechanism of CO<sub>2</sub> reduction on these catalysts. The results suggest that the limiting potentials for CO generation on s-Ni<sub>3</sub>@BN and e-Ni<sub>3</sub>@BN are as low as −0.13 V and −0.21 V, respectively. Moreover, e-Co<sub>3</sub>@BN is a highly efficient electrocatalyst for C1 product formation, with limiting potentials for producing CO, HCHO, CH<sub>3</sub>OH, and CH<sub>4</sub> of −0.35 V, −0.46 V, −0.46 V, and −0.46 V, respectively</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"604 ","pages":"Article 113091"},"PeriodicalIF":2.4,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974263","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}
Pub Date : 2026-01-12DOI: 10.1016/j.chemphys.2026.113088
Dragomir Stanisavljev , Annette Fiona Taylor , Itana Nuša Bubanja
The role of surface tension in developing oxidation branch of the Bray-Liebhafsky (BL) oscillatory reaction was investigated. When initiated, its jump-like rate is inhibited by the concentration of the main oxidant showing that it is not solely controlled by chemical processes. It is found that this peculiar rate may be discussed from the perspective of the changes of surface tension of water, caused by main reactants. Obtained results support the idea that gas nucleation (i.e. heterogeneous effects) plays an important role in BL dynamics. Additionally, coupling between nucleation and chemical reactions is perceived from the formalism of non-equilibrium thermodynamics.
{"title":"The role of surface tension on development of oxidation bursts in the self-organizing Bray-Liebhafsky reaction","authors":"Dragomir Stanisavljev , Annette Fiona Taylor , Itana Nuša Bubanja","doi":"10.1016/j.chemphys.2026.113088","DOIUrl":"10.1016/j.chemphys.2026.113088","url":null,"abstract":"<div><div>The role of surface tension in developing oxidation branch of the Bray-Liebhafsky (BL) oscillatory reaction was investigated. When initiated, its jump-like rate is inhibited by the concentration of the main oxidant showing that it is not solely controlled by chemical processes. It is found that this peculiar rate may be discussed from the perspective of the changes of surface tension of water, caused by main reactants. Obtained results support the idea that gas nucleation (<em>i.e.</em> heterogeneous effects) plays an important role in BL dynamics. Additionally, coupling between nucleation and chemical reactions is perceived from the formalism of non-equilibrium thermodynamics.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"604 ","pages":"Article 113088"},"PeriodicalIF":2.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974262","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}
Pub Date : 2026-01-12DOI: 10.1016/j.chemphys.2026.113089
Sofia Yakhnenko, Victor Kostjukov
The nonfluorescent dye phenol blue (PB) is known in fundamental physicochemical research primarily for its strong solvatochromism. The primary objective of this DFT/TD-DFT study was to elucidate the contribution of specific interactions of the dye with a highly polar solvent to its solvatochromic behavior. For this purpose, a comparative analysis of a single PB molecule and a set of its hydrated complexes was performed, in both the ground and excited states. CAM-B3LYP was selected from a set of hybrid functionals as it provided the best agreement between the calculated dipole moment in the ground state and the experimental one. Electron density shifts were analyzed for the complete photochemical cycle of PB. Their key feature turned out to be double forward and reverse charge transfers between the electron donor (dimethylamino group) and the acceptor (carbonyl group). A mutual influence of the dye's H-bond acceptors (the oxygen atom and the central nitrogen atom) was also found due to electronic cooperativity and modifications in local electrostatic potential. This limits their simultaneous hydration in the ground state. When optimizing the excited states of ten hydrate complexes stable in the ground state, two of them were destroyed. Nine of them exhibited a bathochromic shift (relative to a single hydration PB molecule) with increased intermolecular H-bonding to water in excited states. Moreover, with equal overall hydration indices, water binding to the oxygen atom produces a greater bathochromic shift than nitrogen atom hydration. It was also found that PB hydration significantly influences photoinduced distortions of its structure.
{"title":"Theoretical analysis of the absorption of phenol blue dye in aqueous solution: the mutual influence of hydration and excitation","authors":"Sofia Yakhnenko, Victor Kostjukov","doi":"10.1016/j.chemphys.2026.113089","DOIUrl":"10.1016/j.chemphys.2026.113089","url":null,"abstract":"<div><div>The nonfluorescent dye phenol blue (PB) is known in fundamental physicochemical research primarily for its strong solvatochromism. The primary objective of this DFT/TD-DFT study was to elucidate the contribution of specific interactions of the dye with a highly polar solvent to its solvatochromic behavior. For this purpose, a comparative analysis of a single PB molecule and a set of its hydrated complexes was performed, in both the ground and excited states. CAM-B3LYP was selected from a set of hybrid functionals as it provided the best agreement between the calculated dipole moment in the ground state and the experimental one. Electron density shifts were analyzed for the complete photochemical cycle of PB. Their key feature turned out to be double forward and reverse charge transfers between the electron donor (dimethylamino group) and the acceptor (carbonyl group). A mutual influence of the dye's H-bond acceptors (the oxygen atom and the central nitrogen atom) was also found due to electronic cooperativity and modifications in local electrostatic potential. This limits their simultaneous hydration in the ground state. When optimizing the excited states of ten hydrate complexes stable in the ground state, two of them were destroyed. Nine of them exhibited a bathochromic shift (relative to a single hydration PB molecule) with increased intermolecular H-bonding to water in excited states. Moreover, with equal overall hydration indices, water binding to the oxygen atom produces a greater bathochromic shift than nitrogen atom hydration. It was also found that PB hydration significantly influences photoinduced distortions of its structure.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"604 ","pages":"Article 113089"},"PeriodicalIF":2.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974261","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}
Pub Date : 2026-01-10DOI: 10.1016/j.chemphys.2026.113087
Zegang Wang, Jiacai Chen, Yuli Di, Hongcheng Luo, Jifeng Liu
Strong metal-ligand interaction is critical for designing advanced materials. Herein, density functional theory (DFT) is employed to investigate binding characteristics of five divalent transition-metal ions (Mn2+, Fe2+, Co2+, Ni2+, Cu2+) toward three Schiff base-benzene ligands (mSBB, dSBB and tSBB). Mn2+, Fe2+, Co2+ and Ni2+ can adopt both benzene-proximal mode and imine-proximal binding mode, whereas Cu2+ shows a pronounced preference for the imine-proximal binding mode. Binding energies computed with multiple DFT functionals are exceptionally large (130–310 kcal/mol) and increase with metal atomic number. Notably, the imine-proximal binding mode yields higher binding energies than the benzene-proximal binding mode. Experimental validation using Cu2+-mSBB structure incorporated into an elastomer demonstrates that the strong Cu2+-mSBB binding significantly enhances both tensile strength and toughness, while maintaining high recyclability. Moreover, the resulting material exhibits antibacterial activity. These results elucidate strong transition metal/Schiff base-benzene interactions and guide rational design of high-performance sports materials.
{"title":"Strong transition metal/Schiff Base-benzene interactions enhance strength, toughness, and recyclability of elastomers for sport applications","authors":"Zegang Wang, Jiacai Chen, Yuli Di, Hongcheng Luo, Jifeng Liu","doi":"10.1016/j.chemphys.2026.113087","DOIUrl":"10.1016/j.chemphys.2026.113087","url":null,"abstract":"<div><div>Strong metal-ligand interaction is critical for designing advanced materials. Herein, density functional theory (DFT) is employed to investigate binding characteristics of five divalent transition-metal ions (Mn<sup>2+</sup>, Fe<sup>2+</sup>, Co<sup>2+</sup>, Ni<sup>2+</sup>, Cu<sup>2+</sup>) toward three Schiff base-benzene ligands (mSBB, dSBB and tSBB). Mn<sup>2+</sup>, Fe<sup>2+</sup>, Co<sup>2+</sup> and Ni<sup>2+</sup> can adopt both benzene-proximal mode and imine-proximal binding mode, whereas Cu<sup>2+</sup> shows a pronounced preference for the imine-proximal binding mode. Binding energies computed with multiple DFT functionals are exceptionally large (130–310 kcal/mol) and increase with metal atomic number. Notably, the imine-proximal binding mode yields higher binding energies than the benzene-proximal binding mode. Experimental validation using Cu<sup>2+</sup>-mSBB structure incorporated into an elastomer demonstrates that the strong Cu<sup>2+</sup>-mSBB binding significantly enhances both tensile strength and toughness, while maintaining high recyclability. Moreover, the resulting material exhibits antibacterial activity. These results elucidate strong transition metal/Schiff base-benzene interactions and guide rational design of high-performance sports materials.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"604 ","pages":"Article 113087"},"PeriodicalIF":2.4,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034834","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}
Pub Date : 2026-01-07DOI: 10.1016/j.chemphys.2026.113079
Hao Liu , Xing-Han Li , Zheng-Tang Liu , Wen-Guang Li
The electronic, vibrational, thermodynamic, and detonation properties of Difurazo(3,4-h;3,4-l)-1,4,7,10,11-trioxadiazacyclotridec-10-ene (DFTE) crystal were studied using density functional theory (DFT) in first principles calculations. The phonon spectrum of DFTE indicates its dynamic stability; In addition, we discussed in detail the significant vibration peaks and their corresponding vibration modes in Raman and infrared spectra. Based on vibration characteristics, thermodynamic functions such as Helmholtz free energy (F), heat capacity (CV), etc. were calculated and discussed within the range of 0-1000 K. The initial estimate shows that the explosion heat (Q) of DFTE is 4989.2 kJ/kg, the explosion velocity (D) is 7365 m/s, and the explosion pressure (P) is 22.32 GPa. At present, there are no corresponding experimental values for these data. Therefore, understanding these properties will provide reference and guidance for future research.
{"title":"Density functional theory study of the electronic, vibrational, thermodynamic, and detonation properties of Difurazo(3,4-h,3,4-l)-1,4,7,10,11-trioxadiazacyclotridec-10-ene","authors":"Hao Liu , Xing-Han Li , Zheng-Tang Liu , Wen-Guang Li","doi":"10.1016/j.chemphys.2026.113079","DOIUrl":"10.1016/j.chemphys.2026.113079","url":null,"abstract":"<div><div>The electronic, vibrational, thermodynamic, and detonation properties of Difurazo(3,4-h;3,4-l)-1,4,7,10,11-trioxadiazacyclotridec-10-ene (DFTE) crystal were studied using density functional theory (DFT) in first principles calculations. The phonon spectrum of DFTE indicates its dynamic stability; In addition, we discussed in detail the significant vibration peaks and their corresponding vibration modes in Raman and infrared spectra. Based on vibration characteristics, thermodynamic functions such as Helmholtz free energy (F), heat capacity (C<sub>V</sub>), etc. were calculated and discussed within the range of 0-1000 K. The initial estimate shows that the explosion heat (Q) of DFTE is 4989.2 kJ/kg, the explosion velocity (D) is 7365 m/s, and the explosion pressure (P) is 22.32 GPa. At present, there are no corresponding experimental values for these data. Therefore, understanding these properties will provide reference and guidance for future research.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"604 ","pages":"Article 113079"},"PeriodicalIF":2.4,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034830","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}
Pub Date : 2026-01-03DOI: 10.1016/j.chemphys.2026.113078
Huifang Xu , Song Lu , Jingya Zhang , Sijia Wang , Chenyu Zhao , Bin Liu , Yuanyuan Li
Recently, we have reported the vesicle formation and vesicle-to-micelle transition (VMT) of sodium 2-ketooctanoate, a single-tailed keto-acid salt, in water with increasing concentration. Herein, we demonstrate that, upon prolonged standing at the vesicle-forming concentration, macroscopic fibrous structures spontaneously formed. Cryogenic transmission electron microscopy, atomic force microscopy, and laser scanning confocal microscopy revealed the microscopic pathway: vesicles aggregated and evolved through elongated intermediate structures (threadlike vesicles and chains of vesicles) into long strips, which ultimately assembled into floating fibers. As concentration was increased around the critical micelle concentration (CMC), these fibers transformed into bundles of nanofibers and threadlike micelles, and finally evolved to globular micelles above the CMC. The observed multi-step aggregation behavior is driven by the dynamic coexistence and rearrangement of multiple species, notably “acid-soap” dimers. This constitutes the first report detailing the microscopic transition pathway from fibrous structures to micelles for a single-tailed keto-acid salt amphiphile in water.
{"title":"Transition from fibrous structures to micelles of sodium 2-ketooctanoate with increasing concentration in water","authors":"Huifang Xu , Song Lu , Jingya Zhang , Sijia Wang , Chenyu Zhao , Bin Liu , Yuanyuan Li","doi":"10.1016/j.chemphys.2026.113078","DOIUrl":"10.1016/j.chemphys.2026.113078","url":null,"abstract":"<div><div>Recently, we have reported the vesicle formation and vesicle-to-micelle transition (VMT) of sodium 2-ketooctanoate, a single-tailed keto-acid salt, in water with increasing concentration. Herein, we demonstrate that, upon prolonged standing at the vesicle-forming concentration, macroscopic fibrous structures spontaneously formed. Cryogenic transmission electron microscopy, atomic force microscopy, and laser scanning confocal microscopy revealed the microscopic pathway: vesicles aggregated and evolved through elongated intermediate structures (threadlike vesicles and chains of vesicles) into long strips, which ultimately assembled into floating fibers. As concentration was increased around the critical micelle concentration (CMC), these fibers transformed into bundles of nanofibers and threadlike micelles, and finally evolved to globular micelles above the CMC. The observed multi-step aggregation behavior is driven by the dynamic coexistence and rearrangement of multiple species, notably “acid-soap” dimers. This constitutes the first report detailing the microscopic transition pathway from fibrous structures to micelles for a single-tailed keto-acid salt amphiphile in water.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"604 ","pages":"Article 113078"},"PeriodicalIF":2.4,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145940274","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}
The work investigates the optical properties of organic materials based on linear derivatives of thiazolo[2,3-b]quinazoline in solutions and films using UV–Vis spectroscopy. The energy gap (Egap) was determined using the Tauc method, and quantum chemical calculations (DFT, B3LYP/TZVP) were performed for comparison with experimental data. It is shown that compounds of this class are characterized by direct allowed transitions. It was found that the Egap values for solutions range from 3.11 to 4.21 eV, and for films from 2.78 to 3.72 eV. The lowest band gap values were recorded for thiazolo[2,3-b]quinazolinium triiodides. The calculated values are in good agreement with the experimental ones (discrepancy 0.81–15 %), which confirms the hypothesis of the directly allowed nature of transitions. The influence of solvation on Egap values in solutions has been revealed. The results obtained are important for predicting the photophysical and photochemical properties of quinazoline derivatives and their application in optoelectronics and materials science.
{"title":"Experimental and theoretical approach to determining the nature of energy transitions in linear halogen- and chalcogen-functionalized derivatives of thiazolo[2,3-b]quinazolines","authors":"Diana Kut , Ruslan Mariychuk , Artem Pogodin , Mykola Kut","doi":"10.1016/j.chemphys.2025.113077","DOIUrl":"10.1016/j.chemphys.2025.113077","url":null,"abstract":"<div><div>The work investigates the optical properties of organic materials based on linear derivatives of thiazolo[2,3-<em>b</em>]quinazoline in solutions and films using UV–Vis spectroscopy. The energy gap (E<sub>gap</sub>) was determined using the Tauc method, and quantum chemical calculations (DFT, B3LYP/TZVP) were performed for comparison with experimental data. It is shown that compounds of this class are characterized by direct allowed transitions. It was found that the E<sub>gap</sub> values for solutions range from 3.11 to 4.21 eV, and for films from 2.78 to 3.72 eV. The lowest band gap values were recorded for thiazolo[2,3-<em>b</em>]quinazolinium triiodides. The calculated values are in good agreement with the experimental ones (discrepancy 0.81–15 %), which confirms the hypothesis of the directly allowed nature of transitions. The influence of solvation on E<sub>gap</sub> values in solutions has been revealed. The results obtained are important for predicting the photophysical and photochemical properties of quinazoline derivatives and their application in optoelectronics and materials science.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"604 ","pages":"Article 113077"},"PeriodicalIF":2.4,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145940273","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}
Pub Date : 2025-12-30DOI: 10.1016/j.chemphys.2025.113076
S.A. Shehzad , F. Mustafa , A. Rauf , H.M. Imran , T. Mushtaq
Maxwell fluids are non-Newtonian fluids of special type which exhibit a unique behavior subject to shear stress. Maxwell fluids provide insights into industrial applications dealing with polymeric fluids, rotating machinery and various chemical processes. The present study examines the flow aspects of Maxwell fluid over a rotating disk. A similarity transformation approach is employed to transform the governing flow model into a system of nonlinear ordinary differential equations. The reduced system of equations is then solved using Runge-Kutta-Fehlberg (RKF-45) method. The results on velocity temperature, and concentration profiles against flow parameters are obtained and discussed graphically. The numerical values such as shear stresses, heat transfer rate, and mass transfer rate are calculated at the disk surface and are displayed in tabular format. We also employed Generalized Additive Model (GAM) to study the impact of respective physical parameters on local Nusselt number and Sherwood number.
{"title":"Generalized additive model (GAM) for magnetized Maxwell fluid flow over a rotating disk with endothermic/exothermic chemical reactions","authors":"S.A. Shehzad , F. Mustafa , A. Rauf , H.M. Imran , T. Mushtaq","doi":"10.1016/j.chemphys.2025.113076","DOIUrl":"10.1016/j.chemphys.2025.113076","url":null,"abstract":"<div><div>Maxwell fluids are non-Newtonian fluids of special type which exhibit a unique behavior subject to shear stress. Maxwell fluids provide insights into industrial applications dealing with polymeric fluids, rotating machinery and various chemical processes. The present study examines the flow aspects of Maxwell fluid over a rotating disk. A similarity transformation approach is employed to transform the governing flow model into a system of nonlinear ordinary differential equations. The reduced system of equations is then solved using Runge-Kutta-Fehlberg (RKF-45) method. The results on velocity temperature, and concentration profiles against flow parameters are obtained and discussed graphically. The numerical values such as shear stresses, heat transfer rate, and mass transfer rate are calculated at the disk surface and are displayed in tabular format. We also employed Generalized Additive Model (GAM) to study the impact of respective physical parameters on local Nusselt number and Sherwood number.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"604 ","pages":"Article 113076"},"PeriodicalIF":2.4,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882724","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}
Pub Date : 2025-12-27DOI: 10.1016/j.chemphys.2025.113075
Qaiser Rafiq, Nadia Qaiser
A detailed First-principles study is conducted in this research to discuss the effect of substituting Eu and Tb on the structural, electronic, optical, magnetic, thermodynamic, mechanical, and thermoelectric properties of Sb2Se3. These calculations are done using the FP-LAPW method used in WIEN2k using the GGA + U + SOC functional because it can adequately describe anisotropic SbSe bonding and the localization of the rare-earth 4f states. All of the systems studied are stable in the orthorhombic Pnma phase and only show minor lattice distortions, which support the structural compatibility of Eu3+ and Tb3+ in the host lattice Sb2 Se3. Incorporation of the rare-earths causes significant changes in the electronic structure: Eu substitution gives rise to a spin-polarized narrow-bandgap state, which is a semiconductor; Tb substitution produces strong 4f -p interactions that substantially rearrange the band dispersion. The optical response is changed accordingly with increased low-energy absorption as well as changes in dielectric behavior. According to the magnetic results, as a transition of a parent compound of non-magnetic nature, a paramagnetic state with non-cooperative 4f moments at localized and stable magnetic moments occurred. In addition, elastic and thermodynamic studies show that doping leads to a higher lattice rigidity, phonon activity, and thermal stability. Transport computations show that a substitution of Eu and Tb allows a tuning of carrier effective masses, Seebeck coefficients, and power factors. The major contribution of the work is unified correlation of these various properties under a single theoretical framework that provides experimentally testable predictions, and has predictive value of rare-earth doping as one of the viable routes to make multifunctional Sb2 Se3 based optoelectronic, thermoelectric and spin-related devices.
本研究采用第一性原理详细研究了取代Eu和Tb对Sb2Se3的结构、电子、光学、磁性、热力学、力学和热电性能的影响。这些计算使用了WIEN2k中使用的FP-LAPW方法，使用GGA + U + SOC函数，因为它可以充分描述各向异性SbSe键和稀土4f态的局域化。所有研究的体系在正交Pnma相中都是稳定的，并且只有轻微的晶格畸变，这支持了Eu3+和Tb3+在主晶格Sb2 Se3中的结构相容性。稀土元素的掺入引起了电子结构的显著变化：铕取代产生自旋极化窄带隙态，这是半导体；Tb取代产生了强的4f -p相互作用，使能带色散重新排列。光学响应随着低能量吸收的增加以及介电行为的变化而相应改变。根据磁性结果，作为非磁性母化合物的一个过渡，在局域磁矩处出现了具有非合作4f矩的顺磁性状态。此外，弹性和热力学研究表明，掺杂导致更高的晶格刚性，声子活性和热稳定性。输运计算表明，替换Eu和Tb可以调整载流子有效质量、塞贝克系数和功率因数。本工作的主要贡献是将这些不同性质统一在一个理论框架下，提供了实验可测试的预测，并且具有预测价值，稀土掺杂是制造多功能Sb2 Se3基光电、热电和自旋相关器件的可行途径之一。
{"title":"First-principles investigation of structural, electronic, optical, thermoelectric, and mechanical properties of Eu- and Tb-doped Sb₂Se₃","authors":"Qaiser Rafiq, Nadia Qaiser","doi":"10.1016/j.chemphys.2025.113075","DOIUrl":"10.1016/j.chemphys.2025.113075","url":null,"abstract":"<div><div>A detailed First-principles study is conducted in this research to discuss the effect of substituting Eu and Tb on the structural, electronic, optical, magnetic, thermodynamic, mechanical, and thermoelectric properties of Sb<sub>2</sub>Se<sub>3</sub>. These calculations are done using the FP-LAPW method used in WIEN2k using the GGA + U + SOC functional because it can adequately describe anisotropic SbSe bonding and the localization of the rare-earth 4f states. All of the systems studied are stable in the orthorhombic Pnma phase and only show minor lattice distortions, which support the structural compatibility of Eu<sup>3+</sup> and Tb<sup>3+</sup> in the host lattice Sb<sub>2</sub> Se<sub>3</sub>. Incorporation of the rare-earths causes significant changes in the electronic structure: Eu substitution gives rise to a spin-polarized narrow-bandgap state, which is a semiconductor; Tb substitution produces strong 4f -p interactions that substantially rearrange the band dispersion. The optical response is changed accordingly with increased low-energy absorption as well as changes in dielectric behavior. According to the magnetic results, as a transition of a parent compound of non-magnetic nature, a paramagnetic state with non-cooperative 4f moments at localized and stable magnetic moments occurred. In addition, elastic and thermodynamic studies show that doping leads to a higher lattice rigidity, phonon activity, and thermal stability. Transport computations show that a substitution of Eu and Tb allows a tuning of carrier effective masses, Seebeck coefficients, and power factors. The major contribution of the work is unified correlation of these various properties under a single theoretical framework that provides experimentally testable predictions, and has predictive value of rare-earth doping as one of the viable routes to make multifunctional Sb<sub>2</sub> Se<sub>3</sub> based optoelectronic, thermoelectric and spin-related devices.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"604 ","pages":"Article 113075"},"PeriodicalIF":2.4,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882723","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}
Pub Date : 2025-12-24DOI: 10.1016/j.chemphys.2025.113074
Hossien Hossieni
We propose a new analytical potential function to model proton transfer in the adenine–thymine base pair and develop a non-adiabatic quantum mechanical framework to calculate genetic mutation probabilities. This potential has been used to calculate the probability of mutation in a non-adiabatic process. The results of the new model have been shown to be consistent with the findings of other researchers.
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