Pub Date : 2025-12-05DOI: 10.1016/j.chemphys.2025.113054
Jiangyang Qin , Hong Zhang , Bo Ma , Xinlu Cheng
The interaction of defects in energetic materials(EMs) has been extensively investigated using continuum-scale simulations. However, such approaches inherently struggle to capture processes occurring at the atomic or molecular level. In this study, we offer an atomistic perspective to explore the potential mechanisms by which nanodefect distributions in RDX influence hotspot temperature under strong shock loading. Simulation results reveal that due to the effect of Mach Stem, a significant concentration of kinetic energy occurs in the downstream region within the double-defect model. In the triple-defect model, This kinetic energy concentration further amplifies the shock wave at the third defect, significantly increasing the local temperature and thereby accelerating the chemical reaction rate. This finding indicates that under strong shock loading, there are strong interactions between nanodefects within RDX, which can significantly affect hotspot temperatures. Specifically, the local temperature in the triple-defect model is 586.7 K higher than in the single-defect model.
{"title":"Interaction mechanism of RDX nanodefects under strong shock loading and the enhancement of hotspot temperature: A reactive atomistic perspective","authors":"Jiangyang Qin , Hong Zhang , Bo Ma , Xinlu Cheng","doi":"10.1016/j.chemphys.2025.113054","DOIUrl":"10.1016/j.chemphys.2025.113054","url":null,"abstract":"<div><div>The interaction of defects in energetic materials(EMs) has been extensively investigated using continuum-scale simulations. However, such approaches inherently struggle to capture processes occurring at the atomic or molecular level. In this study, we offer an atomistic perspective to explore the potential mechanisms by which nanodefect distributions in RDX influence hotspot temperature under strong shock loading. Simulation results reveal that due to the effect of Mach Stem, a significant concentration of kinetic energy occurs in the downstream region within the double-defect model. In the triple-defect model, This kinetic energy concentration further amplifies the shock wave at the third defect, significantly increasing the local temperature and thereby accelerating the chemical reaction rate. This finding indicates that under strong shock loading, there are strong interactions between nanodefects within RDX, which can significantly affect hotspot temperatures. Specifically, the local temperature in the triple-defect model is 586.7 K higher than in the single-defect model.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113054"},"PeriodicalIF":2.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733044","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 : 2025-12-05DOI: 10.1016/j.chemphys.2025.113053
Kaito Sasaki , K.P. Safna Hussan , Rio Kita , Takeru Ito , Yosuke Okamura , Naoki Shinyashiki
Polyvinylpyrrolidone (PVP) is a widely used synthetic polymer known for its versatility, biocompatibility, solubility, and thermal stability, with applications spanning pharmaceuticals, biomedicine, food, cosmetics, and electronics. Despite its broad usage, detailed insights into its dynamic behavior remain limited. This study presents a comprehensive investigation of the structural, dynamic, and spectroscopic properties of bulk PVP (molecular weight of 10,000 g/mol) using a multi-scale approach that combines Density Functional Theory (DFT), thermal analysis with Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA), and experimental spectroscopic techniques with Broadband Dielectric Spectroscopy (BDS) and Fourier Transform Infrared (FTIR) spectroscopy. DFT calculations reveal that polymerization significantly enhances reactivity, polarity, solubility, and a reduction in bandgap (from 7.19 to 3.95 eV). FTIR spectra further confirm hydrogen bonding interactions. DSC analysis indicates a glass transition temperature (Tg) of 396 K, while thermal stability extends up to ∼660 K. BDS over a wide frequency (10−2 to 107 Hz) and temperature (178–473 K) range identifies three distinct relaxation processes: α-relaxation associated with cooperative segmental motion related to the glass transition phenomenon, β-relaxation attributed to Johari-Goldstein dynamics, and γ-relaxation linked to localized side-chain motions. The fragility index (m = 46) obtained from the temperature dependence of relaxation time of the α-relaxation classifies PVP as a strong glass former, with excellent structural and thermal resilience. These findings offer fundamental insights into PVP's dynamic behavior and reinforce its potential across diverse high-performance applications.
{"title":"Fundamental insights into bulk polyvinylpyrrolidone (PVP): Combining DFT, molecular dynamics, and spectroscopic techniques","authors":"Kaito Sasaki , K.P. Safna Hussan , Rio Kita , Takeru Ito , Yosuke Okamura , Naoki Shinyashiki","doi":"10.1016/j.chemphys.2025.113053","DOIUrl":"10.1016/j.chemphys.2025.113053","url":null,"abstract":"<div><div>Polyvinylpyrrolidone (PVP) is a widely used synthetic polymer known for its versatility, biocompatibility, solubility, and thermal stability, with applications spanning pharmaceuticals, biomedicine, food, cosmetics, and electronics. Despite its broad usage, detailed insights into its dynamic behavior remain limited. This study presents a comprehensive investigation of the structural, dynamic, and spectroscopic properties of bulk PVP (molecular weight of 10,000 g/mol) using a multi-scale approach that combines Density Functional Theory (DFT), thermal analysis with Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA), and experimental spectroscopic techniques with Broadband Dielectric Spectroscopy (BDS) and Fourier Transform Infrared (FTIR) spectroscopy. DFT calculations reveal that polymerization significantly enhances reactivity, polarity, solubility, and a reduction in bandgap (from 7.19 to 3.95 eV). FTIR spectra further confirm hydrogen bonding interactions. DSC analysis indicates a glass transition temperature (<em>T</em><sub><em>g</em></sub>) of 396 K, while thermal stability extends up to ∼660 K. BDS over a wide frequency (10<sup>−2</sup> to 10<sup>7</sup> Hz) and temperature (178–473 K) range identifies three distinct relaxation processes: α-relaxation associated with cooperative segmental motion related to the glass transition phenomenon, β-relaxation attributed to Johari-Goldstein dynamics, and γ-relaxation linked to localized side-chain motions. The fragility index (m = 46) obtained from the temperature dependence of relaxation time of the α-relaxation classifies PVP as a strong glass former, with excellent structural and thermal resilience. These findings offer fundamental insights into PVP's dynamic behavior and reinforce its potential across diverse high-performance applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113053"},"PeriodicalIF":2.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733040","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}
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.
{"title":"Exploring the multifaceted properties of Cs2LiBiX6 (X = F, Br) perovskites for next generation optoelectronic devices","authors":"Md. Minhajul Abedin Nannu , Md. Sharif Uddin , Md. Rubayed Hasan Pramanik , Abdullah Marzouq Alharbi , Nacer Badi , Aijaz Rasool Chaudhry , Ahmad Irfan , 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":"2025-12-03","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}
We investigated the physical properties of K₂CaH₄ under 0–15 GPa using first-principles calculations. The lattice parameters are a = b = 4.4148 Å, c = 14.1434 Å, with formation enthalpy −0.4001 eV atom-1 and cohesive energy 2.85 eV atom-1. The elastic constants satisfy the mechanical-stability criteria. Electronic band gaps are wide, decreasing slightly with pressure (3.38 eV at 0 GPa to 3.23 eV at 15 GPa), identifying K₂CaH₄ as an insulator. Phonon dispersions show no imaginary modes up to 10 GPa and the onset of instability at 15 GPa. The Debye temperature rises from 388.04 K (0 GPa) to 419.88 K (10 GPa) and then drops to 352.59 K (15 GPa). Optically, the maximum absorption coefficient reaches 5.59 × 105 cm-1 at 35.58 eV, and peak reflectivity increases to 69%. Hydrogen-storage metrics are a gravimetric capacity of 2.86 wt% and a volumetric capacity of 48.17 gH₂L-1.
用第一性原理计算研究了K₂CaH₄在0-15 GPa条件下的物理性质。晶格参数为a = b = 4.4148 Å， c = 14.1434 Å，形成焓为−0.4001 eV原子-1，结合能为2.85 eV原子-1。弹性常数满足力学稳定性准则。电子带隙较宽，随压力的增大而减小（0 GPa时为3.38 eV， 15 GPa时为3.23 eV），表明K₂CaH₄为绝缘体。声子色散在10gpa以下无虚模，在15gpa时开始失稳。德拜温度从388.04 K （0 GPa）上升到419.88 K (10 GPa)，然后下降到352.59 K （15 GPa）。光学上，在35.58 eV下，最大吸收系数达到5.59 × 105 cm-1，峰值反射率增加到69%。储氢指标的重量容量为2.86 wt%，体积容量为48.17 gH₂L-1。
{"title":"Investigation on structural, mechanical, electronic, vibrational, thermophysical, optic, and hydrogen storage properties of K2CaH4 under pressures from 0 to 15 GPa","authors":"Çağatay Yamçıçıer , Cihan Kürkçü , Sümeyra Yamçıçıer","doi":"10.1016/j.chemphys.2025.113039","DOIUrl":"10.1016/j.chemphys.2025.113039","url":null,"abstract":"<div><div>We investigated the physical properties of K₂CaH₄ under 0–15 GPa using first-principles calculations. The lattice parameters are <em>a</em> = <em>b =</em> 4.4148 Å, <em>c</em> = 14.1434 Å, with formation enthalpy −0.4001 eV atom<sup>-1</sup> and cohesive energy 2.85 eV atom<sup>-1</sup>. The elastic constants satisfy the mechanical-stability criteria. Electronic band gaps are wide, decreasing slightly with pressure (3.38 eV at 0 GPa to 3.23 eV at 15 GPa), identifying K₂CaH₄ as an insulator. Phonon dispersions show no imaginary modes up to 10 GPa and the onset of instability at 15 GPa. The Debye temperature rises from 388.04 K (0 GPa) to 419.88 K (10 GPa) and then drops to 352.59 K (15 GPa). Optically, the maximum absorption coefficient reaches 5.59 × 10<sup>5</sup> cm<sup>-1</sup> at 35.58 eV, and peak reflectivity increases to 69%. Hydrogen-storage metrics are a gravimetric capacity of 2.86 wt% and a volumetric capacity of 48.17 gH₂L<sup>-1</sup>.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113039"},"PeriodicalIF":2.4,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681696","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}
Half Heusler (hH) compounds have demonstrated great potential for high-temperature thermoelectric applications, offering significant promise for addressing global energy challenges. This study comprehensively analyzes the structural, electronic, magnetic, dynamical, mechanical, and thermoelectric properties of 18-valence-electron count (VEC) hH’s XIrPb (X= V, Nb, Ta), using density functional theory (DFT), and semi-classical Boltzmann transport theory (BTE). Because of the presence of heavier elements Pb and Ir, the spin–orbit coupling effects were considered in all calculations. All three compounds exhibit thermodynamic, dynamical, and mechanical stability, with ductile characteristics. The compounds are non-magnetic semiconductors with indirect band gaps of 0.16 eV, 0.58 eV, and 0.93 eV for VIrPb, NbIrPb, and TaIrPb, respectively. XIrPb have low lattice thermal conductivity ( 10 Wm−1K−1) at room temperature. The p-type doping exhibits superior thermoelectric performance compared to n-type doping, with an optimal value of 1.51 for VIrPb at 900 K, whereas NbIrPb and TaIrPb show maximum values of 1.39 and 1.38 at 1100 K, respectively. In conclusion, this study highlights all of the hole-doped compounds with as promising materials for high-temperature thermoelectric power generation.
{"title":"First-principles study of half Heusler XIrPb (X= V, Nb, Ta) for energy applications","authors":"Govinda Gaire , Nabin Regmi , Kashi Ram Panday , Prakash Khatri , Narayan Prasad Adhikari","doi":"10.1016/j.chemphys.2025.113040","DOIUrl":"10.1016/j.chemphys.2025.113040","url":null,"abstract":"<div><div>Half Heusler (hH) compounds have demonstrated great potential for high-temperature thermoelectric applications, offering significant promise for addressing global energy challenges. This study comprehensively analyzes the structural, electronic, magnetic, dynamical, mechanical, and thermoelectric properties of 18-valence-electron count (VEC) hH’s XIrPb (X= V, Nb, Ta), using density functional theory (DFT), and semi-classical Boltzmann transport theory (BTE). Because of the presence of heavier elements Pb and Ir, the spin–orbit coupling effects were considered in all calculations. All three compounds exhibit thermodynamic, dynamical, and mechanical stability, with ductile characteristics. The compounds are non-magnetic semiconductors with indirect band gaps of 0.16 eV, 0.58 eV, and 0.93 eV for VIrPb, NbIrPb, and TaIrPb, respectively. XIrPb have low lattice thermal conductivity ( <span><math><mo><</mo></math></span> 10 Wm<sup>−1</sup>K<sup>−1</sup>) at room temperature. The p-type doping exhibits superior thermoelectric performance compared to n-type doping, with an optimal <span><math><mrow><mi>z</mi><mi>T</mi></mrow></math></span> value of 1.51 for VIrPb at 900 K, whereas NbIrPb and TaIrPb show maximum <span><math><mrow><mi>z</mi><mi>T</mi></mrow></math></span> values of 1.39 and 1.38 at 1100 K, respectively. In conclusion, this study highlights all of the hole-doped compounds with <span><math><mrow><mi>z</mi><mi>T</mi><mo>></mo><mn>1</mn></mrow></math></span> as promising materials for high-temperature thermoelectric power generation.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113040"},"PeriodicalIF":2.4,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145616153","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 : 2025-11-25DOI: 10.1016/j.chemphys.2025.113038
A. Bourfoune , L.B. Drissi
To address berberine’s low bioavailability and Dose-Limiting Toxicity, we loaded it onto a hexagonal -Gy (-graphyne) quantum dot, known as graphyne spoked wheel, and analyzed the complex via DFT calculations. Adsorption energy in the gas phase (–1.70 eV) confirms effective drug loading. Furthermore, thermodynamic values ( = –2.18 eV, = –1.36 eV) show exothermic, spontaneous binding under physiological conditions. Negative adsorption energy in water suggest stability during bloodstream circulation without premature release. Moreover, the increased dipole moments (up to 14.02 D) imply enhanced mobility and solubility, while FMO, DOS, and PDOS analyses reveal charge transfer from berberine to the dot. QTAIM, ELF and NCI analyses demonstrate noncovalent interactions that support controlled release. Functionalization with amine (NH) and carboxyl (COOH) groups adds pH sensitivity: significant binding at physiological pH, and shifts to 2.32 eV in acidic tumor environments, enabling targeted release. These results support functionalized -graphyne as a pH-responsive nanocarrier for precision cancer drug delivery.
{"title":"DFT study of functionalized γ-graphyne quantum dot as pH-sensitive nanocarrier for berberine anticancer drug","authors":"A. Bourfoune , L.B. Drissi","doi":"10.1016/j.chemphys.2025.113038","DOIUrl":"10.1016/j.chemphys.2025.113038","url":null,"abstract":"<div><div>To address berberine’s low bioavailability and Dose-Limiting Toxicity, we loaded it onto a hexagonal <span><math><mi>γ</mi></math></span>-Gy (<span><math><mi>γ</mi></math></span>-graphyne) quantum dot, known as graphyne spoked wheel, and analyzed the complex via DFT calculations. Adsorption energy in the gas phase (–1.70 eV) confirms effective drug loading. Furthermore, thermodynamic values (<span><math><mrow><mi>Δ</mi><mi>H</mi></mrow></math></span> = –2.18 eV, <span><math><mrow><mi>Δ</mi><mi>G</mi></mrow></math></span> = –1.36 eV) show exothermic, spontaneous binding under physiological conditions. Negative adsorption energy in water suggest stability during bloodstream circulation without premature release. Moreover, the increased dipole moments (up to 14.02 D) imply enhanced mobility and solubility, while FMO, DOS, and PDOS analyses reveal charge transfer from berberine to the dot. QTAIM, ELF and NCI analyses demonstrate noncovalent interactions that support controlled release. Functionalization with amine (NH<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>) and carboxyl (COOH) groups adds pH sensitivity: significant binding at physiological pH, and shifts to 2.32 eV in acidic tumor environments, enabling targeted release. These results support functionalized <span><math><mi>γ</mi></math></span>-graphyne as a pH-responsive nanocarrier for precision cancer drug delivery.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113038"},"PeriodicalIF":2.4,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681697","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 : 2025-11-24DOI: 10.1016/j.chemphys.2025.113032
Jianming Ma , Kai Diao , Yiping Yuan , Shunping Shi , Deliang Chen
Based on DFT calculations at the PBE0-D3/def2-TZVP level, this study investigated the lowest energy structures obtained in this study of Ptn+ (n = 3–9) clusters, water molecule adsorption on their surfaces, and the HER mechanism. Water molecules preferentially adsorbed at the top sites of all clusters (adsorption energies: −1.24 to −2.64 eV, exothermic), with Pt₈+ and Pt₉+ exhibiting the highest adsorption energies. For HER, the Pt7+ system required the fewest steps (only 2), while Pt₈+ needed the most (9 steps). Pt3+-Pt7+ showed endothermic behavior (reaction energies: 0.41–1.91 eV), whereas Pt₈+ and Pt9+ were exothermic (−0.47 eV and − 0.71 eV, respectively), with Pt9+ having the most feasible pathway. Except for Pt7+, other systems formed Pt-H-Pt or Pt-O-Pt bonds; Pt3+/Pt4+/Pt7+ stayed stable, others distorted. This study provides a theoretical reference for designing high-efficiency Pt-based catalysts for water splitting.
{"title":"Hydrogen evolution reaction mechanism of Ptn+@H2O (n = 3–9) complexes: A DFT study","authors":"Jianming Ma , Kai Diao , Yiping Yuan , Shunping Shi , Deliang Chen","doi":"10.1016/j.chemphys.2025.113032","DOIUrl":"10.1016/j.chemphys.2025.113032","url":null,"abstract":"<div><div>Based on DFT calculations at the PBE0-D3/def2-TZVP level, this study investigated the lowest energy structures obtained in this study of Pt<sub>n</sub><sup>+</sup> (<em>n</em> = 3–9) clusters, water molecule adsorption on their surfaces, and the HER mechanism. Water molecules preferentially adsorbed at the top sites of all clusters (adsorption energies: −1.24 to −2.64 eV, exothermic), with Pt₈<sup>+</sup> and Pt₉<sup>+</sup> exhibiting the highest adsorption energies. For HER, the Pt<sub>7</sub><sup>+</sup> system required the fewest steps (only 2), while Pt₈<sup>+</sup> needed the most (9 steps). Pt<sub>3</sub><sup>+</sup>-Pt<sub>7</sub><sup>+</sup> showed endothermic behavior (reaction energies: 0.41–1.91 eV), whereas Pt₈<sup>+</sup> and Pt<sub>9</sub><sup>+</sup> were exothermic (−0.47 eV and − 0.71 eV, respectively), with Pt<sub>9</sub><sup>+</sup> having the most feasible pathway. Except for Pt<sub>7</sub><sup>+</sup>, other systems formed Pt-H-Pt or Pt-O-Pt bonds; Pt<sub>3</sub><sup>+</sup>/Pt<sub>4</sub><sup>+</sup>/Pt<sub>7</sub><sup>+</sup> stayed stable, others distorted. This study provides a theoretical reference for designing high-efficiency Pt-based catalysts for water splitting.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113032"},"PeriodicalIF":2.4,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145616296","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 : 2025-11-23DOI: 10.1016/j.chemphys.2025.113036
Liang Zhao , Ke Han , Wenbao Liu , Shucheng Liu , Qi Zhang , Jing Gao
Conventional collectors used in hematite reverse flotation often suffer from poor selectivity and low-temperature instability. In this study, N-lauroylsarcosine sodium (NLSS), an amino acid-based surfactant with carboxyl and amide groups, was utilized as a collector for hematite reverse flotation. Flotation tests showed that NLSS demonstrated superior performance compared to conventional collectors. Under optimal conditions, the hematite grade increased from 59.77 % to 67.11 %, and recovery increased from 87.37 % to 97.33 %. This selectivity was supported by FTIR analysis, contact angle measurements, and zeta potential measurements, which confirmed that NLSS adsorbed onto the quartz surface and significantly enhanced its hydrophobicity. XPS analysis and density functional theory (DFT) calculations further revealed that the good collecting power of NLSS was attributed to multisite binding with Ca(II) sites on the quartz surface. This study demonstrates that multisite reaction strategy can offer a new insight into enhancing hematite reverse flotation performance.
{"title":"A multisite reaction strategy for improving separation performance of hematite reverse flotation by using an amino acid-based collector","authors":"Liang Zhao , Ke Han , Wenbao Liu , Shucheng Liu , Qi Zhang , Jing Gao","doi":"10.1016/j.chemphys.2025.113036","DOIUrl":"10.1016/j.chemphys.2025.113036","url":null,"abstract":"<div><div>Conventional collectors used in hematite reverse flotation often suffer from poor selectivity and low-temperature instability. In this study, N-lauroylsarcosine sodium (NLSS), an amino acid-based surfactant with carboxyl and amide groups, was utilized as a collector for hematite reverse flotation. Flotation tests showed that NLSS demonstrated superior performance compared to conventional collectors. Under optimal conditions, the hematite grade increased from 59.77 % to 67.11 %, and recovery increased from 87.37 % to 97.33 %. This selectivity was supported by FTIR analysis, contact angle measurements, and zeta potential measurements, which confirmed that NLSS adsorbed onto the quartz surface and significantly enhanced its hydrophobicity. XPS analysis and density functional theory (DFT) calculations further revealed that the good collecting power of NLSS was attributed to multisite binding with Ca(II) sites on the quartz surface. This study demonstrates that multisite reaction strategy can offer a new insight into enhancing hematite reverse flotation performance.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113036"},"PeriodicalIF":2.4,"publicationDate":"2025-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145616143","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 : 2025-11-23DOI: 10.1016/j.chemphys.2025.113037
Uzma Sattar , Zeeshan Ali , Godefroid Gahungu , Wenliang Li , Jingping Zhang
Electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) determine the efficiency of electrochemical water splitting. Therefore, we designed a series of multimetallic metal-organic frameworks (MOFs), NH2-BDC-TM3 and Br-BDC-TM3 (NH2-BDC = 2-aminoterephthalate, Br-BDC = 2,5-dibromoterephthalate), as bifunctional electrocatalysts for efficient HER and OER. This study computationally investigated the synergistic effect between metal atoms and substituent groups (NH2 and Br) within the main framework TM3-BDC. All three homonuclear (TM = Fe, Co, Ni) and three Fe-containing heteronuclear (TM3 = Fe2Co, Fe2Ni, FeCoNi) electrocatalysts designed for each (NH2 and Br) substituent group exhibit good stability. The minimum overpotential of NH2-BDC-Fe*CoNi (0.20 V) for OER, and HER (NH2-BDC-Fe2Ni, 0.02 V, O active site) represents that the NH2 substituent is most effective towards OER and HER activity among all the designed catalysts. Br-BDC-Fe*CoNi proved to be a highly efficient as a bifunctional electrocatalyst for OER and HER, with measured overpotentials of 0.45 and 0.18 V, respectively. Our investigation highlights the potential of an active class of MOF electrocatalysts for HER and OER.
{"title":"Enhancing HER and OER through the synergetic effect of metal and ligand in a metal-organic framework, a density functional theory study","authors":"Uzma Sattar , Zeeshan Ali , Godefroid Gahungu , Wenliang Li , Jingping Zhang","doi":"10.1016/j.chemphys.2025.113037","DOIUrl":"10.1016/j.chemphys.2025.113037","url":null,"abstract":"<div><div>Electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) determine the efficiency of electrochemical water splitting. Therefore, we designed a series of multimetallic metal-organic frameworks (MOFs), NH<sub>2</sub>-BDC-TM<sub>3</sub> and Br-BDC-TM<sub>3</sub> (NH<sub>2</sub>-BDC = 2-aminoterephthalate, Br-BDC = 2,5-dibromoterephthalate), as bifunctional electrocatalysts for efficient HER and OER. This study computationally investigated the synergistic effect between metal atoms and substituent groups (NH<sub>2</sub> and Br) within the main framework TM<sub>3</sub>-BDC. All three homonuclear (TM = Fe, Co, Ni) and three Fe-containing heteronuclear (TM<sub>3</sub> = Fe<sub>2</sub>Co, Fe<sub>2</sub>Ni, FeCoNi) electrocatalysts designed for each (NH<sub>2</sub> and Br) substituent group exhibit good stability. The minimum overpotential of NH<sub>2</sub>-BDC-Fe*CoNi (0.20 V) for OER, and HER (NH<sub>2</sub>-BDC-Fe<sub>2</sub>Ni, 0.02 V, O active site) represents that the <img>NH<sub>2</sub> substituent is most effective towards OER and HER activity among all the designed catalysts. Br-BDC-Fe*CoNi proved to be a highly efficient as a bifunctional electrocatalyst for OER and HER, with measured overpotentials of 0.45 and 0.18 V, respectively. Our investigation highlights the potential of an active class of MOF electrocatalysts for HER and OER.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113037"},"PeriodicalIF":2.4,"publicationDate":"2025-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681706","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}
Cancer treatment is one of most concerning topics, however, it is limited by factors such as low selectivity and multiple drug resistance currently, so there is an urgent need for developing new therapies. This study focuses on the potential anti-cancer peptide (ACP) FLAK50 and analyzes its interaction with the cancer cell membrane through molecular dynamics simulation, as well as the impact of amino acid residue rearrangement/replacement on activity and the characteristics of the lipid bilayer system. The results show that the phenylpropanoid amino acid residues are the key head groups for membrane interaction; ACP can reduce the thickness of the cancer cell model membrane, increase the lipid area, and cause abnormal diffusion of POPS, and has a stronger targeting effect on cancer cell membranes containing POPS. The conclusion reveals the core mechanism of ACP - membrane interaction, confirms its potential as an optimization strategy for cancer treatment, and provides theoretical support for the development of new anti-cancer therapies.
{"title":"Interaction mechanism of FLAK50 anticancer peptide with phospholipid bilayer membranes: Molecular dynamics investigation","authors":"Hongxiu Yuan, Yongkang Lyu, Changzhe Zhang, Qingtian Meng","doi":"10.1016/j.chemphys.2025.113033","DOIUrl":"10.1016/j.chemphys.2025.113033","url":null,"abstract":"<div><div>Cancer treatment is one of most concerning topics, however, it is limited by factors such as low selectivity and multiple drug resistance currently, so there is an urgent need for developing new therapies. This study focuses on the potential anti-cancer peptide (ACP) FLAK50 and analyzes its interaction with the cancer cell membrane through molecular dynamics simulation, as well as the impact of amino acid residue rearrangement/replacement on activity and the characteristics of the lipid bilayer system. The results show that the phenylpropanoid amino acid residues are the key head groups for membrane interaction; ACP can reduce the thickness of the cancer cell model membrane, increase the lipid area, and cause abnormal diffusion of POPS, and has a stronger targeting effect on cancer cell membranes containing POPS. The conclusion reveals the core mechanism of ACP - membrane interaction, confirms its potential as an optimization strategy for cancer treatment, and provides theoretical support for the development of new anti-cancer therapies.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113033"},"PeriodicalIF":2.4,"publicationDate":"2025-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145616152","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号