Pub Date : 2025-10-17DOI: 10.1016/j.chemphys.2025.112974
Monalisha Nayak, Ranjan K. Singh
The clinically important drug gabapentin (GBP) exhibits polymorphism, crystallizing in multiple forms (α, β and γ) that differ in molecular packing and spectroscopic signatures. The α, β and γ polymorphs of GBP have been extensively examined through temperature-dependent Raman spectroscopy and density functional theory (DFT) analysis. Temperature-dependent Raman spectra suggested the polymorphic phase transitions with temperature. The α form is predominant at room temperature. The α → β phase transition is observed at ∼150 °C and β → γ phase transition is observed at∼170 °C. These results imply that GBP possesses many different polymorphs, reflecting many conformational states accessible to the molecule. Surface-enhanced Raman spectroscopy (SERS) measurements of GBP in aqueous medium and human serum enable the direct identification of the β-conformer both upon hydration and within the complex biological matrix.
{"title":"DFT and temperature-dependent Raman spectroscopic study of gabapentin polymorphism and determination of its dominant conformer in human serum","authors":"Monalisha Nayak, Ranjan K. Singh","doi":"10.1016/j.chemphys.2025.112974","DOIUrl":"10.1016/j.chemphys.2025.112974","url":null,"abstract":"<div><div>The clinically important drug gabapentin (GBP) exhibits polymorphism, crystallizing in multiple forms (α, β and γ) that differ in molecular packing and spectroscopic signatures. The α, β and γ polymorphs of GBP have been extensively examined through temperature-dependent Raman spectroscopy and density functional theory (DFT) analysis. Temperature-dependent Raman spectra suggested the polymorphic phase transitions with temperature. The α form is predominant at room temperature. The α → β phase transition is observed at ∼150 °C and β → γ phase transition is observed at∼170 °C. These results imply that GBP possesses many different polymorphs, reflecting many conformational states accessible to the molecule. Surface-enhanced Raman spectroscopy (SERS) measurements of GBP in aqueous medium and human serum enable the direct identification of the β-conformer both upon hydration and within the complex biological matrix.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112974"},"PeriodicalIF":2.4,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-17DOI: 10.1016/j.chemphys.2025.112971
Z. Mongashti, S.M. Azami
Chlorinated hydrocarbons are one of the most widely used compounds in industry, while leading to biological hazards that have attracted the attention of environmental researchers. This research investigates confinement of these compounds in fullerene and its effects on chemical and electronic properties. Various parameters, including bonding, interaction and deformation energies, deformation density, and fullerene ellipticity, were investigated, and results indicated how confinement results in compression of the chlorinated hydrocarbon structure and expansion of fullerene to ellipsoidal form. Energetic analyses revealed that the confinement process is non-spontaneous, endothermic, and species are thermodynamically unstable, where by increasing the number of chlorine substitutions, values of these energies also increase.
{"title":"Protection of chlorinated hydrocarbon as host-guest complex inside C60 fullerene","authors":"Z. Mongashti, S.M. Azami","doi":"10.1016/j.chemphys.2025.112971","DOIUrl":"10.1016/j.chemphys.2025.112971","url":null,"abstract":"<div><div>Chlorinated hydrocarbons are one of the most widely used compounds in industry, while leading to biological hazards that have attracted the attention of environmental researchers. This research investigates confinement of these compounds in fullerene and its effects on chemical and electronic properties. Various parameters, including bonding, interaction and deformation energies, deformation density, and fullerene ellipticity, were investigated, and results indicated how confinement results in compression of the chlorinated hydrocarbon structure and expansion of fullerene to ellipsoidal form. Energetic analyses revealed that the confinement process is non-spontaneous, endothermic, and species are thermodynamically unstable, where by increasing the number of chlorine substitutions, values <!--> <!-->of these energies also increase.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112971"},"PeriodicalIF":2.4,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-17DOI: 10.1016/j.chemphys.2025.112977
Yayun Hu , Hongxia Wang , Jing Lu, Xin Chen, Kangyu Jia, Dong Wang
Polyamide (PA)-based reverse osmosis (RO) membranes are pivotal in water treatment due to their superior separation performance and cost-effectiveness. Nevertheless, challenges such as membrane fouling and the permeability-selectivity trade-off limit their efficiency. This study employs molecular dynamics simulations and density functional theory to systematically investigate the influence of sulfonamide chain length on the performances of PA-based RO membranes. Three sulfonamide-modified PA membranes (M-AESA(n), n = 2, 4, 6) were constructed to assess morphology, hydrophilicity, water transport dynamics, antifouling behavior, and salt resistance. Results demonstrate that increasing sulfonamide chain length enhances membrane roughness, hydrophilicity, and fractional free volume, correlating with improved water diffusion coefficients and flux. Notably, M-AESA(4) exhibits optimal antifouling capability owing to weakened interfacial interactions with calcium alginate foulants. All modified membranes retain robust salt rejection under simulated conditions. These findings provide molecular-level insights into the design of high-performance PA-based membranes, bridging theoretical predictions with practical membrane optimization strategies.
聚酰胺（PA）基反渗透（RO）膜由于其优越的分离性能和成本效益在水处理中起着关键作用。然而，膜污染和渗透性-选择性权衡等挑战限制了它们的效率。本研究采用分子动力学模拟和密度泛函理论，系统研究了磺胺链长对pa基反渗透膜性能的影响。构建了三种磺胺修饰的PA膜（M-AESA(n), n = 2, 4, 6），以评估其形态，亲水性，水运输动力学，防污性能和耐盐性。结果表明，磺胺链长度的增加提高了膜的粗糙度、亲水性和自由体积分数，这与水扩散系数和通量的提高有关。值得注意的是，M-AESA(4)表现出最佳的防污能力，因为它与海藻酸钙污染物的界面相互作用减弱。在模拟条件下，所有改性膜都保持了强大的防盐性能。这些发现为高性能pa基膜的设计提供了分子水平的见解，将理论预测与实际的膜优化策略联系起来。
{"title":"Theoretical insights into sulfonamide chain length effects on polyamide-based reverse osmosis membranes","authors":"Yayun Hu , Hongxia Wang , Jing Lu, Xin Chen, Kangyu Jia, Dong Wang","doi":"10.1016/j.chemphys.2025.112977","DOIUrl":"10.1016/j.chemphys.2025.112977","url":null,"abstract":"<div><div>Polyamide (PA)-based reverse osmosis (RO) membranes are pivotal in water treatment due to their superior separation performance and cost-effectiveness. Nevertheless, challenges such as membrane fouling and the permeability-selectivity trade-off limit their efficiency. This study employs molecular dynamics simulations and density functional theory to systematically investigate the influence of sulfonamide chain length on the performances of PA-based RO membranes. Three sulfonamide-modified PA membranes (M-AESA(<em>n</em>), <em>n</em> = 2, 4, 6) were constructed to assess morphology, hydrophilicity, water transport dynamics, antifouling behavior, and salt resistance. Results demonstrate that increasing sulfonamide chain length enhances membrane roughness, hydrophilicity, and fractional free volume, correlating with improved water diffusion coefficients and flux. Notably, M-AESA(4) exhibits optimal antifouling capability owing to weakened interfacial interactions with calcium alginate foulants. All modified membranes retain robust salt rejection under simulated conditions. These findings provide molecular-level insights into the design of high-performance PA-based membranes, bridging theoretical predictions with practical membrane optimization strategies.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112977"},"PeriodicalIF":2.4,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-14DOI: 10.1016/j.chemphys.2025.112972
D.M. Hoat , Nguyen Thi Han , Chu Viet Ha , Nguyen Quang Hai , J. Guerrero-Sanchez
In this work, the impacts of chalcogen vacancies and doping with transition metals (Mn and Fe), as well as their complexes, on the electronic and magnetic properties of Janus monolayer WSeTe are investigated using first-principles calculations. Pristine monolayer has good structural stability and exhibits the direct-gap semiconductor nature with a band gap of 1.34 eV. The band gap reductions of the order of 19.40% and 23.88% are obtained by creating single Se and Te vacancies, respectively. Mn doping induces magnetic semiconductor nature with the in-plane magnetic anisotropy (IMA), while the half-metallicity with perpendicular magnetic anisotropy (PMA) is obtained by Fe doping. Further, the effects of vacancy+impurity complexes are examined. Calculations suggest the enhanced magnetic anisotropy of Mn- and Fe-doped WSeTe monolayer by means of creating additional single vacancies. In all cases, magnetic properties are produced primarily by orbital of Mn and Fe atoms, where smaller contributions from the host W, Se, and Te atoms are also observed. Importantly, the antiparallel spin coupling between Mn/Fe and W-Se-Te atoms is confirmed. In addition, the calculated cohesive energies and ab initio molecular dynamics (AIMD) simulations confirm good structural stability of all the defected/doped WSeTe systems, suggesting their experimental feasibility. Our findings may introduce efficient methods to induce magnetism in Janus monolayer WSeTe with feature-rich electronic natures towards spintronic applications.
{"title":"A systematic investigation on chalcogen vacancies, doping with transition metals, and their complexes in Janus monolayer WSeTe","authors":"D.M. Hoat , Nguyen Thi Han , Chu Viet Ha , Nguyen Quang Hai , J. Guerrero-Sanchez","doi":"10.1016/j.chemphys.2025.112972","DOIUrl":"10.1016/j.chemphys.2025.112972","url":null,"abstract":"<div><div>In this work, the impacts of chalcogen vacancies and doping with transition metals (Mn and Fe), as well as their complexes, on the electronic and magnetic properties of Janus monolayer WSeTe are investigated using first-principles calculations. Pristine monolayer has good structural stability and exhibits the direct-gap semiconductor nature with a band gap of 1.34 eV. The band gap reductions of the order of 19.40% and 23.88% are obtained by creating single Se and Te vacancies, respectively. Mn doping induces magnetic semiconductor nature with the in-plane magnetic anisotropy (IMA), while the half-metallicity with perpendicular magnetic anisotropy (PMA) is obtained by Fe doping. Further, the effects of vacancy+impurity complexes are examined. Calculations suggest the enhanced magnetic anisotropy of Mn- and Fe-doped WSeTe monolayer by means of creating additional single vacancies. In all cases, magnetic properties are produced primarily by <span><math><mrow><mn>3</mn><mi>d</mi></mrow></math></span> orbital of Mn and Fe atoms, where smaller contributions from the host W, Se, and Te atoms are also observed. Importantly, the antiparallel spin coupling between Mn/Fe and W-Se-Te atoms is confirmed. In addition, the calculated cohesive energies and <em>ab initio</em> molecular dynamics (AIMD) simulations confirm good structural stability of all the defected/doped WSeTe systems, suggesting their experimental feasibility. Our findings may introduce efficient methods to induce magnetism in Janus monolayer WSeTe with feature-rich electronic natures towards spintronic applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112972"},"PeriodicalIF":2.4,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320920","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-13DOI: 10.1016/j.chemphys.2025.112968
Rhuiago Mendes Oliveira , Cassius Marcellus Costa Carvalho , João Batista Lopes Martins , Fernando Pirani , José Roberto dos Santos Politi , Ricardo Gargano
This work focuses on an accurate theoretical characterization of the strength, range, and nature of the weak intermolecular interaction that controls the formation of CH CH, CH N, and CH Ar gaseous dimers. It also provides a reliable valuation of the thermodynamic stability of such three adducts and of their relative distribution of populated intermolecular vibrational levels. The formation of these dimers is driven by the negative components of enthalpy and entropy, indicating that these complexes form nonspontaneously through gas-phase collisions. The results also suggest that the main interaction contribution controlling the stability of these adducts is the dispersion attraction. Furthermore, the formation of the CH CH complex, driven by the stronger interaction, exhibits the least positive free energy variation over a wide range of considered temperatures. The obtained information is of relevance since it opens up a range of applications in several areas, including chemistry, materials science, and astrophysics.
{"title":"Dimers involving methane: Strength, range, and nature of the intermolecular interaction and their thermodynamic stability in gas-phase","authors":"Rhuiago Mendes Oliveira , Cassius Marcellus Costa Carvalho , João Batista Lopes Martins , Fernando Pirani , José Roberto dos Santos Politi , Ricardo Gargano","doi":"10.1016/j.chemphys.2025.112968","DOIUrl":"10.1016/j.chemphys.2025.112968","url":null,"abstract":"<div><div>This work focuses on an accurate theoretical characterization of the strength, range, and nature of the weak intermolecular interaction that controls the formation of CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> <img>CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>, CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> <img>N<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>, and CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> <img>Ar gaseous dimers. It also provides a reliable valuation of the thermodynamic stability of such three adducts and of their relative distribution of populated intermolecular vibrational levels. The formation of these dimers is driven by the negative components of enthalpy and entropy, indicating that these complexes form nonspontaneously through gas-phase collisions. The results also suggest that the main interaction contribution controlling the stability of these adducts is the dispersion attraction. Furthermore, the formation of the CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> <img>CH<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> complex, driven by the stronger interaction, exhibits the least positive free energy variation over a wide range of considered temperatures. The obtained information is of relevance since it opens up a range of applications in several areas, including chemistry, materials science, and astrophysics.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112968"},"PeriodicalIF":2.4,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320885","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-11DOI: 10.1016/j.chemphys.2025.112970
Junjie Zhang, Haixia Chen, Jijun Ding, Yongfeng Qu, Haiwei Fu
The superhydrophobic membranes with low-cost, eco-friendly, and high-performance is a current research focus. In this paper, ZIF-8 particles are synthesized at room temperature and subsequently mixed with graphene oxide with controlled proportions. The resulting composite membrane is fabricated on a fibrous substrate via vacuum filtration. By tailoring the surface microstructure, the wettability of the composite film is effectively modulated. Experimental results demonstrate that the membrane exhibits superhydrophobicity, with a water contact angle of 156° and a separation flux of 31,428.77 L·m−2·h−1 for low-viscosity oils. The membrane shows excellent separation efficiency (>99 %) across oils with varying viscosities. Furthermore, the separation performance remains stable, with efficiency above 99 % after 20 cycles and above 98 % after a 30-day long-term test. The combination of facile preparation, environmental friendliness, and outstanding separation performance highlights the potential of this composite membrane for low-cost, high-efficiency oil-water separation applications.
{"title":"Superhydrophobic ZIF-8-based fibrous membranes for highly effective oil-water separation","authors":"Junjie Zhang, Haixia Chen, Jijun Ding, Yongfeng Qu, Haiwei Fu","doi":"10.1016/j.chemphys.2025.112970","DOIUrl":"10.1016/j.chemphys.2025.112970","url":null,"abstract":"<div><div>The superhydrophobic membranes with low-cost, eco-friendly, and high-performance is a current research focus. In this paper, ZIF-8 particles are synthesized at room temperature and subsequently mixed with graphene oxide with controlled proportions. The resulting composite membrane is fabricated on a fibrous substrate via vacuum filtration. By tailoring the surface microstructure, the wettability of the composite film is effectively modulated. Experimental results demonstrate that the membrane exhibits superhydrophobicity, with a water contact angle of 156° and a separation flux of 31,428.77 L·m<sup>−2</sup>·h<sup>−1</sup> for low-viscosity oils. The membrane shows excellent separation efficiency (>99 %) across oils with varying viscosities. Furthermore, the separation performance remains stable, with efficiency above 99 % after 20 cycles and above 98 % after a 30-day long-term test. The combination of facile preparation, environmental friendliness, and outstanding separation performance highlights the potential of this composite membrane for low-cost, high-efficiency oil-water separation applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112970"},"PeriodicalIF":2.4,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320880","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-11DOI: 10.1016/j.chemphys.2025.112969
Mucahit Enes Atabey , Nazli Oncer , Asli Yilmaz , Yuksel Akinay , Sinan Egri , Ozlem Egri , Mehmet Yilmaz
Medical complications associated with wounds result in significant issues that incur billions of dollars in global costs. Consequently, the development of wound dressing materials that are both cost-effective and efficient is becoming increasingly important. This study introduces the concept of utilizing polydopamine (PDA)-assisted silver nanoparticle (AgNP) decoration on polycaprolactone (PCL) electrospun nanofiber (NF) membranes as a robust wound dressing material. The hydrophobicity of PCL NFs was substantially reduced by the PDA layer, which also improved cell adhesion and exhibited tunable antibacterial activity. This adaptable method enabled the precise regulation of the number density and morphology of decorated AgNPs. The morphology, deposition procedure, and content of the AgNPs partially influenced the ultimate bioactivity of the material. We believe that the NF@PDA@AgNP systems will provide unique benefits as an optimal wound dressing material due to their biodegradability, high antibacterial activity, and minimal cytotoxicity.
{"title":"Silver nanostructure-decorated electrospun polycaprolactone Fibers as a potential wound dressing material","authors":"Mucahit Enes Atabey , Nazli Oncer , Asli Yilmaz , Yuksel Akinay , Sinan Egri , Ozlem Egri , Mehmet Yilmaz","doi":"10.1016/j.chemphys.2025.112969","DOIUrl":"10.1016/j.chemphys.2025.112969","url":null,"abstract":"<div><div>Medical complications associated with wounds result in significant issues that incur billions of dollars in global costs. Consequently, the development of wound dressing materials that are both cost-effective and efficient is becoming increasingly important. This study introduces the concept of utilizing polydopamine (PDA)-assisted silver nanoparticle (AgNP) decoration on polycaprolactone (PCL) electrospun nanofiber (NF) membranes as a robust wound dressing material. The hydrophobicity of PCL NFs was substantially reduced by the PDA layer, which also improved cell adhesion and exhibited tunable antibacterial activity. This adaptable method enabled the precise regulation of the number density and morphology of decorated AgNPs. The morphology, deposition procedure, and content of the AgNPs partially influenced the ultimate bioactivity of the material. We believe that the NF@PDA@AgNP systems will provide unique benefits as an optimal wound dressing material due to their biodegradability, high antibacterial activity, and minimal cytotoxicity.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112969"},"PeriodicalIF":2.4,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of eco-friendly, lead-free perovskites has motivated exploration of vacancy-ordered double perovskites K₂SiX₆ (X = F, Cl, Br). Using DFT with GGA-PBE and HSE06, their structural, electronic, vibrational, mechanical, and optical properties are systematically analyzed. All compounds stabilize in the cubic Fm-3 m phase with tolerance factors within the perovskite stability window. Negative formation energies and phonon spectra without imaginary modes confirm chemical and dynamic stability. Mechanical analysis indicates elastic stability across the series, with K₂SiBr₆ showing the highest stiffness, bulk modulus, and ductility (B/G = 3.015), ensuring strong structural resilience. Electronic calculations reveal a direct 1.14 eV bandgap for K₂SiBr₆, ideally aligned with the Shockley–Queisser efficiency limit. Optical studies highlight enhanced visible absorption, a favorable dielectric constant (ε₁(0) = 5.13), and the lowest energy loss, minimizing recombination. Overall, halide substitution tunes properties, positioning K₂SiBr₆ as a stable, robust, and efficient lead-free candidate for future solar cell applications.
{"title":"Role of halide substitution in K2SiX6 (X = F, cl, Br) perovskites: first-principles insights for sustainable solar cell materials","authors":"Md. Ferdous Rahman , Sirat-E-Azmin Shifa , Tanvir Al Galib , Ahmad Irfan , Aijaz Rasool Chaudhry , Md. Atikur Rahman , Md. Faruk Hossain","doi":"10.1016/j.chemphys.2025.112964","DOIUrl":"10.1016/j.chemphys.2025.112964","url":null,"abstract":"<div><div>The development of eco-friendly, lead-free perovskites has motivated exploration of vacancy-ordered double perovskites K₂SiX₆ (X = F, Cl, Br). Using DFT with GGA-PBE and HSE06, their structural, electronic, vibrational, mechanical, and optical properties are systematically analyzed. All compounds stabilize in the cubic Fm-3 m phase with tolerance factors within the perovskite stability window. Negative formation energies and phonon spectra without imaginary modes confirm chemical and dynamic stability. Mechanical analysis indicates elastic stability across the series, with K₂SiBr₆ showing the highest stiffness, bulk modulus, and ductility (B/G = 3.015), ensuring strong structural resilience. Electronic calculations reveal a direct 1.14 eV bandgap for K₂SiBr₆, ideally aligned with the Shockley–Queisser efficiency limit. Optical studies highlight enhanced visible absorption, a favorable dielectric constant (ε₁(0) = 5.13), and the lowest energy loss, minimizing recombination. Overall, halide substitution tunes properties, positioning K₂SiBr₆ as a stable, robust, and efficient lead-free candidate for future solar cell applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112964"},"PeriodicalIF":2.4,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145320884","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 : 2025-10-09DOI: 10.1016/j.chemphys.2025.112961
Zeinhom M. El Bahy , Taghrid S. Alomar , Najla AlMasoud , Muhammad Abdullah , Tehreem Zahra , Amal A. Al-wallan , Hafiz Muhammad Tahir Farid
{"title":"Corrigendum to “Improved electrocatalytic performance of NdCoO3/rGO for oxygen evolution reaction” [Chem. Phys. 596 (2025) 112774]","authors":"Zeinhom M. El Bahy , Taghrid S. Alomar , Najla AlMasoud , Muhammad Abdullah , Tehreem Zahra , Amal A. Al-wallan , Hafiz Muhammad Tahir Farid","doi":"10.1016/j.chemphys.2025.112961","DOIUrl":"10.1016/j.chemphys.2025.112961","url":null,"abstract":"","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112961"},"PeriodicalIF":2.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145412350","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 : 2025-10-06DOI: 10.1016/j.chemphys.2025.112960
F. Amari , S. Saib , A. Allal
This study presents a comprehensive first-principles investigation of HgSe in its zinc blende (B3) and high-pressure cinnabar (B9) phases, analyzing structural, electronic, elastic, vibrational, and thermodynamic properties using density functional theory. Our calculations reveal a pressure-induced B3 → B9 phase transition at 2.75 GPa (theoretical value) and 0.77 GPa (experimentally calibrated value), with the B9 phase showing anisotropic compressibility and enhanced mechanical stability. Electronic structure calculations with the B3LYP hybrid functional demonstrate that B3-HgSe is a narrow direct-gap semiconductor (0.14 eV at the Γ-point), while B9-HgSe exhibits an indirect gap (1.40 eV), both tunable under pressure. Phonon calculations confirm the dynamical stability of both phases. Thermodynamic properties reveal the B9 phase's superior thermal stability, with a Debye temperature of 162.6 K and ductile mechanical behavior. These findings provide crucial insights into HgSe's potential applications in infrared optoelectronics, pressure sensors, and topological devices, while resolving longstanding discrepancies in previous studies of this complex material system.
{"title":"First-Principles Investigation of Structural, Electronic, Elastic, Vibrational, and Thermodynamic Properties of HgSe in Zinc Blende (B3) and Cinnabar (B9) Phases","authors":"F. Amari , S. Saib , A. Allal","doi":"10.1016/j.chemphys.2025.112960","DOIUrl":"10.1016/j.chemphys.2025.112960","url":null,"abstract":"<div><div>This study presents a comprehensive first-principles investigation of HgSe in its zinc blende (B3) and high-pressure cinnabar (B9) phases, analyzing structural, electronic, elastic, vibrational, and thermodynamic properties using density functional theory. Our calculations reveal a pressure-induced B3 → B9 phase transition at 2.75 GPa (theoretical value) and 0.77 GPa (experimentally calibrated value), with the B9 phase showing anisotropic compressibility and enhanced mechanical stability. Electronic structure calculations with the B3LYP hybrid functional demonstrate that B3-HgSe is a narrow direct-gap semiconductor (0.14 eV at the Γ-point), while B9-HgSe exhibits an indirect gap (1.40 eV), both tunable under pressure. Phonon calculations confirm the dynamical stability of both phases. Thermodynamic properties reveal the B9 phase's superior thermal stability, with a Debye temperature of 162.6 K and ductile mechanical behavior. These findings provide crucial insights into HgSe's potential applications in infrared optoelectronics, pressure sensors, and topological devices, while resolving longstanding discrepancies in previous studies of this complex material system.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"601 ","pages":"Article 112960"},"PeriodicalIF":2.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145262285","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}
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