Pub Date : 2025-12-07DOI: 10.1016/j.chemphys.2025.113057
Ahmad Ali , Shayan Ahmad , Muhammad Hashir , Mohamed Karouchi , Asif Nawaz Khan , Imran Shakir
In this article, the structural, optoelectronic, and thermoelectric properties of novel Sc2BaX₄ (X = S, Se) chalcogenides have been elaborated, utilizing ab initio investigations. The FP-LAPW method incorporated in the WIEN2k code is used to investigate the structural, optoelectronic, and thermoelectric properties of these chalcogenides. The phonon dispersion and mechanical study confirm the dynamical and mechanical stability of the materials. The TB-mBj potential is utilized to achieve accurate electronic band gaps of the materials. The study of the electronic structure reveals that the materials are indirect band semiconductors, with energy band gaps of 1.8 and 1.7 eV for Sc2BaS4 and Sc2BaSe4, respectively. The optical study predicts that the energy absorption is maximum in the visible range of optical spectra. The energy band gaps and optical absorption in the visible range make these materials promising for sustainable energy applications. The Seebeck coefficient of the materials suggests that the Sc2BaS4 is n-type, while Sc2BaSe4 is to be p-type semiconductor at high temperatures.
{"title":"First-principles study of the dynamical, mechanical, optoelectronic, and thermoelectric properties of Sc2BaX4 (X = S, Se) chalcogenides for sustainable energy applications","authors":"Ahmad Ali , Shayan Ahmad , Muhammad Hashir , Mohamed Karouchi , Asif Nawaz Khan , Imran Shakir","doi":"10.1016/j.chemphys.2025.113057","DOIUrl":"10.1016/j.chemphys.2025.113057","url":null,"abstract":"<div><div>In this article, the structural, optoelectronic, and thermoelectric properties of novel Sc<sub>2</sub>BaX₄ (X = S, Se) chalcogenides have been elaborated, utilizing ab initio investigations. The FP-LAPW method incorporated in the WIEN2k code is used to investigate the structural, optoelectronic, and thermoelectric properties of these chalcogenides. The phonon dispersion and mechanical study confirm the dynamical and mechanical stability of the materials. The TB-mBj potential is utilized to achieve accurate electronic band gaps of the materials. The study of the electronic structure reveals that the materials are indirect band semiconductors, with energy band gaps of 1.8 and 1.7 eV for Sc<sub>2</sub>BaS<sub>4</sub> and Sc<sub>2</sub>BaSe<sub>4</sub>, respectively. The optical study predicts that the energy absorption is maximum in the visible range of optical spectra. The energy band gaps and optical absorption in the visible range make these materials promising for sustainable energy applications. The Seebeck coefficient of the materials suggests that the Sc<sub>2</sub>BaS<sub>4 is</sub> n-type, while Sc<sub>2</sub>BaSe<sub>4</sub> is to be p-type semiconductor at high temperatures.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113057"},"PeriodicalIF":2.4,"publicationDate":"2025-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733043","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.2025.113055
Roberto Luiz Andrade Haiduke
The molecular method is used to determine the nuclear quadrupole moments (NQMs) of two barium isotopes, 135Ba and 137Ba. Hence, accurate relativistic electric field gradient (EFG) calculations based on the four-component formalism done at the barium nucleus in two diatomic systems, BaO and BaF, are combined with experimental data of nuclear quadrupole coupling constants. The best EFGs are provided by accounting for electron correlation effects from Dirac-Coulomb Coupled Cluster calculations with iterative single and double excitations plus perturbative triples, with additive Gaunt, vibrational, and extra basis set corrections. Therefore, the recommended NQMs for 135Ba and 137Ba are 155(5) and 239(7) mbarn, respectively.
{"title":"The nuclear quadrupole moment of barium from the molecular method","authors":"Roberto Luiz Andrade Haiduke","doi":"10.1016/j.chemphys.2025.113055","DOIUrl":"10.1016/j.chemphys.2025.113055","url":null,"abstract":"<div><div>The molecular method is used to determine the nuclear quadrupole moments (NQMs) of two barium isotopes, <sup>135</sup>Ba and <sup>137</sup>Ba. Hence, accurate relativistic electric field gradient (EFG) calculations based on the four-component formalism done at the barium nucleus in two diatomic systems, BaO and BaF, are combined with experimental data of nuclear quadrupole coupling constants. The best EFGs are provided by accounting for electron correlation effects from Dirac-Coulomb Coupled Cluster calculations with iterative single and double excitations plus perturbative triples, with additive Gaunt, vibrational, and extra basis set corrections. Therefore, the recommended NQMs for <sup>135</sup>Ba and <sup>137</sup>Ba are 155(5) and 239(7) mbarn, respectively.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113055"},"PeriodicalIF":2.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733041","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-05DOI: 10.1016/j.chemphys.2025.113056
Feng Gu, Jijun Xiao
Organic-inorganic energetic perovskite materials have become a major attraction in the field of energetic materials. Silver-based energetic perovskite (H2pz)[Ag(ClO4)3] (PAP-5) has garnered significant interest due to its unique detonation properties, mechanical, electrical, and structural characteristics. Since strain engineering serves as a powerful tool for modifying the physical properties and crystal structure of perovskite materials, this study employs density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations to investigate the microstructural characteristics of PAP-5 under mechanical loading. The focus includes its structural evolution, band gap, electron charge density, mechanical stability, and interatomic/molecular interactions within the material. It is found that the compressive strength of PAP-5 is greater than the tensile strength, and the stress in different directions is anisotropic. The analysis of bond length and bond angle show that tensile strain has a greater influence on the structure of PAP-5. The band gap will shrink under tensile strain and fluctuate under compressive strain, which is explained from the total density of states. PAP-5 exhibits elastic anisotropy after strain is applied, showing brittleness and ductility during tension and compression respectively. The results of Hirshfeld surface analysis show that the structure of BX3 is more responsive to the applied strain than that of A-site cation.
{"title":"Theoretical study on the effect of strain engineering on the structure and properties of energetic silver-based perovskite","authors":"Feng Gu, Jijun Xiao","doi":"10.1016/j.chemphys.2025.113056","DOIUrl":"10.1016/j.chemphys.2025.113056","url":null,"abstract":"<div><div>Organic-inorganic energetic perovskite materials have become a major attraction in the field of energetic materials. Silver-based energetic perovskite (H<sub>2</sub>pz)[Ag(ClO<sub>4</sub>)<sub>3</sub>] (PAP-5) has garnered significant interest due to its unique detonation properties, mechanical, electrical, and structural characteristics. Since strain engineering serves as a powerful tool for modifying the physical properties and crystal structure of perovskite materials, this study employs density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations to investigate the microstructural characteristics of PAP-5 under mechanical loading. The focus includes its structural evolution, band gap, electron charge density, mechanical stability, and interatomic/molecular interactions within the material. It is found that the compressive strength of PAP-5 is greater than the tensile strength, and the stress in different directions is anisotropic. The analysis of bond length and bond angle show that tensile strain has a greater influence on the structure of PAP-5. The band gap will shrink under tensile strain and fluctuate under compressive strain, which is explained from the total density of states. PAP-5 exhibits elastic anisotropy after strain is applied, showing brittleness and ductility during tension and compression respectively. The results of Hirshfeld surface analysis show that the structure of BX<sub>3</sub> is more responsive to the applied strain than that of A-site cation.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113056"},"PeriodicalIF":2.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733042","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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}
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