Pub Date : 2025-11-21DOI: 10.1016/j.chemphys.2025.113031
Chong-Chong She , Tian-Cheng Zhang , Li-Xiao-Song Du , Peng Wang , Tao Fang , Xiao Ma , Liang Song
The molecular structure of linear polycyclic hydrocarbon makes pentacyclotetradecane (C14H20) a candidate for high energy density fuel, with potential applications as a hydrocarbon fuel for aircraft. Results show that the combustion of C14H20 requires activation energies ranging from 93.14 to 123.37 kJ/mol. The main pathway for the initial decomposition of C14H20 involves the cleavage of CC and CH bonds. A significant amount of C14H20 is consumed by the reaction of C14H20 → 2 C7H10, where the CC bond connecting the two ring compounds is broken and the same ring structure C7H10 is formed. O2, OH, and HO2 contribute significantly to the consumption of C14H20 via pathways such as C14H20 + M → C14H19 + M-H (M = O2, OH, HO2). The ring-opening reactions of C14H20 mainly occur in six-membered rings rather than five-membered rings. Additionally, the consumption and formation pathways of main products such as C2H4, C2H2, and CH2O are detailed.
{"title":"ReaxFF-MD simulations of the oxidation mechanism of pentacyclotetradecane","authors":"Chong-Chong She , Tian-Cheng Zhang , Li-Xiao-Song Du , Peng Wang , Tao Fang , Xiao Ma , Liang Song","doi":"10.1016/j.chemphys.2025.113031","DOIUrl":"10.1016/j.chemphys.2025.113031","url":null,"abstract":"<div><div>The molecular structure of linear polycyclic hydrocarbon makes pentacyclotetradecane (C<sub>14</sub>H<sub>20</sub>) a candidate for high energy density fuel, with potential applications as a hydrocarbon fuel for aircraft. Results show that the combustion of C<sub>14</sub>H<sub>20</sub> requires activation energies ranging from 93.14 to 123.37 kJ/mol. The main pathway for the initial decomposition of C<sub>14</sub>H<sub>20</sub> involves the cleavage of C<img>C and C<img>H bonds. A significant amount of C<sub>14</sub>H<sub>20</sub> is consumed by the reaction of C<sub>14</sub>H<sub>20</sub> → 2 C<sub>7</sub>H<sub>10</sub>, where the C<img>C bond connecting the two ring compounds is broken and the same ring structure C<sub>7</sub>H<sub>10</sub> is formed. O<sub>2</sub>, OH, and HO<sub>2</sub> contribute significantly to the consumption of C<sub>14</sub>H<sub>20</sub> via pathways such as C<sub>14</sub>H<sub>20</sub> + M → C<sub>14</sub>H<sub>19</sub> + M-H (M = O<sub>2</sub>, OH, HO<sub>2</sub>). The ring-opening reactions of C<sub>14</sub>H<sub>20</sub> mainly occur in six-membered rings rather than five-membered rings. Additionally, the consumption and formation pathways of main products such as C<sub>2</sub>H<sub>4</sub>, C<sub>2</sub>H<sub>2</sub>, and CH<sub>2</sub>O are detailed.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113031"},"PeriodicalIF":2.4,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145616142","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 : 2025-11-21DOI: 10.1016/j.chemphys.2025.113035
Navneet Sharma, Kousik Giri
The formation of molecular hydrogen () and its isotopic variants (HD, DH, and D) on a coronene molecule via an Eley-Rideal mechanism is studied using the multiconfiguration time-dependent Hartree method. The calculations are carried out for two- and three-dimensional model systems considering only collinear collisions using a newly developed potential energy surface calculated using the hybrid functional approximation of density functional theory. We report reaction probabilities as a function of collision energy in the range 0–30 meV, relevant to the interstellar medium. The studied reaction is barrierless, leading to a reaction probability close to one, even for low collision energies. We find that the desorbed and its isotopes are vibrationally excited, and the maximum populations at = 3 or 4. The computed vibrational excitation probability values are in good agreement with recent experimental results reported by Latimer et al. (2008) for HD/graphite. The percentage of energy shared by vibration and translation of the product molecule are 42%–62% and 18%–38%, respectively, and 20% of energy is contributed to the surface.
采用多构型时间依赖Hartree方法研究了分子氢（H2）及其同位素变体（HD、DH和D2）在冠烯分子上通过Eley-Rideal机制的形成。利用密度泛函理论的混合泛函近似计算的新发展的势能面，对仅考虑共线碰撞的二维和三维模型系统进行了计算。我们报告了反应概率作为碰撞能量在0-30 meV范围内的函数，与星际介质有关。所研究的反应是无障碍的，即使在低碰撞能量下，反应概率也接近于1。我们发现解吸的H2和它的同位素是振动激发的，在ν = 3或4时最大的居群。计算得到的振动激发概率值与Latimer et al.（2008）最近报道的HD/石墨的实验结果非常吻合。产物分子的振动和平移所共享的能量比例分别为42% ~ 62%和18% ~ 38%，其中20%的能量贡献给了表面。
{"title":"Quantum dynamical study on the formation of molecular hydrogen on a coronene molecule via an Eley-Rideal mechanism","authors":"Navneet Sharma, Kousik Giri","doi":"10.1016/j.chemphys.2025.113035","DOIUrl":"10.1016/j.chemphys.2025.113035","url":null,"abstract":"<div><div>The formation of molecular hydrogen (<span><math><msub><mrow><mi>H</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span>) and its isotopic variants (HD, DH, and D<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>) on a coronene molecule via an Eley-Rideal mechanism is studied using the multiconfiguration time-dependent Hartree method. The calculations are carried out for two- and three-dimensional model systems considering only collinear collisions using a newly developed potential energy surface calculated using the hybrid functional approximation of density functional theory. We report reaction probabilities as a function of collision energy in the range 0–30 meV, relevant to the interstellar medium. The studied reaction is barrierless, leading to a reaction probability close to one, even for low collision energies. We find that the desorbed <span><math><msub><mrow><mi>H</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span> and its isotopes are vibrationally excited, and the maximum populations at <span><math><mi>ν</mi></math></span> = 3 or 4. The computed vibrational excitation probability values are in good agreement with recent experimental results reported by Latimer et al. (2008) for HD/graphite. The percentage of energy shared by vibration and translation of the product molecule are 42%–62% and 18%–38%, respectively, and 20% of energy is contributed to the surface.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113035"},"PeriodicalIF":2.4,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145571119","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 : 2025-11-19DOI: 10.1016/j.chemphys.2025.113030
Qiqi Niu , Yiqi Pan , Ming Chen , Longfei Sun , Kang Zhang , Yun Zhang , Jing Yan , Wei Qi , Lin Yang , Zhaoxia Dong , Xiaochen Li
CO2 foam plays a pivotal role in the synergistic integration of enhanced oil recovery and carbon geological storage, which is attributed to its ability to control CO2 mobility and accelerate CO2 dissolution-mineralization. However, foams are inherently thermodynamically unstable systems. Notably, CO2 not only undergoes inter-bubble diffusion but also dissolves in aqueous phases, collectively exacerbating foam destabilization. Therefore, it is of great significance to optimize the structure of the foam agent for constructing a highly stable CO2 foam system. In this paper, the properties of CO2 bubble film and the arrangement of molecules on the liquid film were studied through experiments and molecular simulations in a series of conventional surfactant solutions. Specifically, the effects of hydrophobic carbon chains and hydrophilic groups of surfactants on liquid film permeability, interfacial adsorption process, bubble stability, and CO2 molecular behavior were analyzed. The lab results show that the CO2 bubbles in systems containing C16-based quaternary ammonium (TAC-16) and betaine (S16) surfactants exhibited lifespans of 186 and 69 min, respectively, representing 85 and 29 times longer than that of C12-based counterparts (TAC-12 and S12). The liquid film permeability of CO2 bubbles in TAC-16 and S16 were 5.02 and 11.99 cm/min, corresponding to 1/7 and 1/3 of TAC-12 and S12. Furthermore, the adsorption capacities of TAC-16 and S16 were 1.63 and 3.06 mol/m2 at the gas-liquid interface, which were greater than those of TAC-12 and S12. Long-chain surfactants had strong hydrophobic interactions, which enhanced their adsorption and micelle formation capabilities. Long-chain surfactants showed a certain affinity for CO2 molecules and could form a dense adsorption layer at the gas-liquid interface. The results indicate that the long-chain surfactants can delay the diffusion and dissolution of CO2 in the liquid film and have obvious advantages as CO2 foam agents. This work preliminarily reveals the molecular states and interactions within CO₂ foams, providing critical insights for designing and developing CO2 foam agents.
{"title":"Effect of molecular structure of surfactants on its behavioral characteristics at the CO2/water interface","authors":"Qiqi Niu , Yiqi Pan , Ming Chen , Longfei Sun , Kang Zhang , Yun Zhang , Jing Yan , Wei Qi , Lin Yang , Zhaoxia Dong , Xiaochen Li","doi":"10.1016/j.chemphys.2025.113030","DOIUrl":"10.1016/j.chemphys.2025.113030","url":null,"abstract":"<div><div>CO<sub>2</sub> foam plays a pivotal role in the synergistic integration of enhanced oil recovery and carbon geological storage, which is attributed to its ability to control CO<sub>2</sub> mobility and accelerate CO<sub>2</sub> dissolution-mineralization. However, foams are inherently thermodynamically unstable systems. Notably, CO<sub>2</sub> not only undergoes inter-bubble diffusion but also dissolves in aqueous phases, collectively exacerbating foam destabilization. Therefore, it is of great significance to optimize the structure of the foam agent for constructing a highly stable CO<sub>2</sub> foam system. In this paper, the properties of CO<sub>2</sub> bubble film and the arrangement of molecules on the liquid film were studied through experiments and molecular simulations in a series of conventional surfactant solutions. Specifically, the effects of hydrophobic carbon chains and hydrophilic groups of surfactants on liquid film permeability, interfacial adsorption process, bubble stability, and CO<sub>2</sub> molecular behavior were analyzed. The lab results show that the CO<sub>2</sub> bubbles in systems containing C16-based quaternary ammonium (TAC-16) and betaine (S16) surfactants exhibited lifespans of 186 and 69 min, respectively, representing 85 and 29 times longer than that of C12-based counterparts (TAC-12 and S12). The liquid film permeability of CO<sub>2</sub> bubbles in TAC-16 and S16 were 5.02 and 11.99 cm/min, corresponding to 1/7 and 1/3 of TAC-12 and S12. Furthermore, the adsorption capacities of TAC-16 and S16 were 1.63 and 3.06 mol/m<sup>2</sup> at the gas-liquid interface, which were greater than those of TAC-12 and S12. Long-chain surfactants had strong hydrophobic interactions, which enhanced their adsorption and micelle formation capabilities. Long-chain surfactants showed a certain affinity for CO<sub>2</sub> molecules and could form a dense adsorption layer at the gas-liquid interface. The results indicate that the long-chain surfactants can delay the diffusion and dissolution of CO<sub>2</sub> in the liquid film and have obvious advantages as CO<sub>2</sub> foam agents. This work preliminarily reveals the molecular states and interactions within CO₂ foams, providing critical insights for designing and developing CO<sub>2</sub> foam agents.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113030"},"PeriodicalIF":2.4,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145571117","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 significant waste heat released from daily fossil fuel combustion contributes to global warming, which thereby necessitates direct waste heat-to-electricity conversion. This work presents a comprehensive first-principles investigation of the electronic, optoelectronic, and thermoelectric properties of the HfRhP half-Heusler compound for efficient energy harvesting. The investigation employed Density Functional Theory within the Generalized Gradient Approximation using the Perdew–Burke–Ernzerhof exchange–correlation functional. The calculations confirm the phase of HfRhP as the most energetically stable, with an equilibrium lattice parameter of and a direct band gap of . From the elastic constants and moduli, HfRhP is found to be ductile and highly resistant to linear compression. HfRhP is mechanically and thermodynamically stable. Seebeck coefficient of HfRhP is and figure of merit () is 0.78. HfRhP has a high absorption coefficient and strong interband transition. These results reveal that HfRhP is high performance thermoelectric and optoelectronic candidate.
{"title":"First-principles calculations to Investigate structural, Electronic, Optoelectronic, and Thermoelectric properties of HfRhP half-Heusler compound","authors":"M.K. Bamgbose , G.T. Solola , O.I. Atobatele , C.O. Ilabija , J.M. Whetode , K.A. Ogunmoye","doi":"10.1016/j.chemphys.2025.113023","DOIUrl":"10.1016/j.chemphys.2025.113023","url":null,"abstract":"<div><div>The significant waste heat released from daily fossil fuel combustion contributes to global warming, which thereby necessitates direct waste heat-to-electricity conversion. This work presents a comprehensive first-principles investigation of the electronic, optoelectronic, and thermoelectric properties of the HfRhP half-Heusler compound for efficient energy harvesting. The investigation employed Density Functional Theory within the Generalized Gradient Approximation using the Perdew–Burke–Ernzerhof exchange–correlation functional. The calculations confirm the <span><math><mi>γ</mi></math></span> phase of HfRhP as the most energetically stable, with an equilibrium lattice parameter of <span><math><mrow><mn>5</mn><mo>.</mo><mn>93</mn><mtext>Å</mtext></mrow></math></span> and a direct band gap of <span><math><mrow><mn>0</mn><mo>.</mo><mn>89</mn><mtext>eV</mtext></mrow></math></span>. From the elastic constants and moduli, HfRhP is found to be ductile and highly resistant to linear compression. HfRhP is mechanically and thermodynamically stable. Seebeck coefficient of HfRhP is <span><math><mrow><mn>531</mn><mo>.</mo><mn>6</mn><mtext></mtext><mi>μ</mi><mtext>V/K</mtext></mrow></math></span> and figure of merit (<span><math><mrow><mi>Z</mi><mi>T</mi></mrow></math></span>) is 0.78. HfRhP has a high absorption coefficient and strong interband transition. These results reveal that HfRhP is high performance thermoelectric and optoelectronic candidate.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113023"},"PeriodicalIF":2.4,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576682","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 : 2025-11-15DOI: 10.1016/j.chemphys.2025.113022
Evren Görkem Özdemir , Wisam Ayad Ahmed Ahmed
The ferromagnetic phases of LiCrZ3 (Z = Cl, Br, I) single perovskites are the most stable magnetic phases. Each single perovskite was obtained as an elastically stable material, and each material was ductile. The total magnetic moment values were obtained as 4.00 μB/f.u. for LiCrZ3. The most partial contributions in each group came from Cr-transition metals. LiCrZ3 materials exhibit a true half-metallic nature, displaying metallic behavior in up-spin orientations and semiconducting behavior in down-spin orientations. Thermodynamic calculations depending on temperature and pressure have been performed. The results of structural, electronic, elastic, and thermodynamic calculations, such as volume, Debye temperatures, and bulk modulus, are consistent. Heat capacity values take their constant values after 300 K for LiCrCl3. While the remarkable electronic, magnetic, elastic, and thermodynamic properties of LiCrZ3 (Z = Cl, Br, I) single perovskites make them suitable for spintronic technologies, their optical properties will also guide their use in optoelectronic technologies.
{"title":"Comprehensive analysis of half-metallic, mechanical, electronic, thermodynamic, and optical properties of single perovskites LiCrZ3 (Z = Cl, Br, I)","authors":"Evren Görkem Özdemir , Wisam Ayad Ahmed Ahmed","doi":"10.1016/j.chemphys.2025.113022","DOIUrl":"10.1016/j.chemphys.2025.113022","url":null,"abstract":"<div><div>The ferromagnetic phases of LiCrZ<sub>3</sub> (Z = Cl, Br, I) single perovskites are the most stable magnetic phases. Each single perovskite was obtained as an elastically stable material, and each material was ductile. The total magnetic moment values were obtained as 4.00 μ<sub>B</sub>/f.u. for LiCrZ<sub>3</sub>. The most partial contributions in each group came from Cr-transition metals. LiCrZ<sub>3</sub> materials exhibit a true half-metallic nature, displaying metallic behavior in up-spin orientations and semiconducting behavior in down-spin orientations. Thermodynamic calculations depending on temperature and pressure have been performed. The results of structural, electronic, elastic, and thermodynamic calculations, such as volume, Debye temperatures, and bulk modulus, are consistent. Heat capacity values take their constant values after 300 K for LiCrCl<sub>3</sub>. While the remarkable electronic, magnetic, elastic, and thermodynamic properties of LiCrZ<sub>3</sub> (Z = Cl, Br, I) single perovskites make them suitable for spintronic technologies, their optical properties will also guide their use in optoelectronic technologies.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113022"},"PeriodicalIF":2.4,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576683","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 : 2025-11-15DOI: 10.1016/j.chemphys.2025.113026
Yanqiao Dong , Junfang Liu
To enhance the performance of bentonite-based barrier systems under heavy metal contamination, this study introduced corn straw biochar as an adsorptive amendment into polymer-modified calcium bentonite, successfully developing a polymer-modified calcium bentonite-biochar composite barrier material (PB8@C8). Through systematic evaluation of compressive strength, permeability coefficient, swell index, and adsorption performance, the optimal biochar content was determined to be 8 %. At this ratio, the material exhibited significant improvements in permeability coefficient, swell index, and adsorption capacity. Although the compressive strength slightly decreased, it still met the engineering requirement of 103.4 kPa. Microstructural characterization techniques such as XRD, SEM, FTIR, and BET confirmed the successful incorporation of biochar into the modified calcium bentonite, introducing abundant hydroxyl and carboxyl functional groups as well as a larger specific surface area, thereby enhancing the adsorption performance. Analysis of the Pb2+ adsorption behavior indicated that the adsorption process of PB8@C8 better conformed to the pseudo-second-order kinetic model and the Langmuir isotherm model, suggesting monolayer chemical adsorption as the dominant mechanism. Under the conditions of pH = 6, an adsorbent dosage of 0.25 g, and an initial Pb2+ concentration of 500 mg/L, the adsorption capacity of PB8@C8 for Pb2+ reached 195.98 mg/g.
{"title":"Adsorption and resistance properties of Pb2+ by modified calcium bentonite @ biochar composite barrier","authors":"Yanqiao Dong , Junfang Liu","doi":"10.1016/j.chemphys.2025.113026","DOIUrl":"10.1016/j.chemphys.2025.113026","url":null,"abstract":"<div><div>To enhance the performance of bentonite-based barrier systems under heavy metal contamination, this study introduced corn straw biochar as an adsorptive amendment into polymer-modified calcium bentonite, successfully developing a polymer-modified calcium bentonite-biochar composite barrier material (PB8@C8). Through systematic evaluation of compressive strength, permeability coefficient, swell index, and adsorption performance, the optimal biochar content was determined to be 8 %. At this ratio, the material exhibited significant improvements in permeability coefficient, swell index, and adsorption capacity. Although the compressive strength slightly decreased, it still met the engineering requirement of 103.4 kPa. Microstructural characterization techniques such as XRD, SEM, FTIR, and BET confirmed the successful incorporation of biochar into the modified calcium bentonite, introducing abundant hydroxyl and carboxyl functional groups as well as a larger specific surface area, thereby enhancing the adsorption performance. Analysis of the Pb<sup>2+</sup> adsorption behavior indicated that the adsorption process of PB8@C8 better conformed to the pseudo-second-order kinetic model and the Langmuir isotherm model, suggesting monolayer chemical adsorption as the dominant mechanism. Under the conditions of pH = 6, an adsorbent dosage of 0.25 g, and an initial Pb<sup>2+</sup> concentration of 500 mg/L, the adsorption capacity of PB8@C8 for Pb<sup>2+</sup> reached 195.98 mg/g.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113026"},"PeriodicalIF":2.4,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576684","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}
Phase transitions of the ionic liquid (IL) with a bulky cation were investigated at low temperature (LT) and high pressure (HP). The IL studied was trihexyl(tetradecyl)phosphonium hexafluorophosphate, [P666,14][PF6]. Upon cooling of 4.6 K/min, LT α phase was formed at 286 K. In the unit cell, void space was visualized. LT crystallization was influenced slightly by the cooling rate. Under HP, the crystal (α-phase) transformed into a flexible crystal (β phase) at 0.7 GPa by reducing void space. The HP α-β phase transition of [P666,14][PF6] was caused by compression of the void space within the unit cell. During the β phase with drastic volume contraction, the void fraction was almost constant. At 4.1 GPa, the flexible β phase transformed to a rigid ionic liquid crystal. Even at the maximum pressure of 7.2 GPa, a reversible volumetric phase transition was observed in the bulky [P666,14][PF6].
{"title":"Volumetric phase transitions in a bulky ionic liquid: trihexyl(tetradecyl)phosphonium hexafluorophosphate","authors":"Hiroshi Abe , Ryo Suzuki , Akihisa Aimi , Hiroaki Kishimura , Daisuke Okuyama , Hajime Sagayama","doi":"10.1016/j.chemphys.2025.113016","DOIUrl":"10.1016/j.chemphys.2025.113016","url":null,"abstract":"<div><div>Phase transitions of the ionic liquid (IL) with a bulky cation were investigated at low temperature (LT) and high pressure (HP). The IL studied was trihexyl(tetradecyl)phosphonium hexafluorophosphate, [P666,14][PF<sub>6</sub>]. Upon cooling of 4.6 K/min, LT α phase was formed at 286 K. In the unit cell, void space was visualized. LT crystallization was influenced slightly by the cooling rate. Under HP, the crystal (α-phase) transformed into a flexible crystal (β phase) at 0.7 GPa by reducing void space. The HP α-β phase transition of [P666,14][PF<sub>6</sub>] was caused by compression of the void space within the unit cell. During the β phase with drastic volume contraction, the void fraction was almost constant. At 4.1 GPa, the flexible β phase transformed to a rigid ionic liquid crystal. Even at the maximum pressure of 7.2 GPa, a reversible volumetric phase transition was observed in the bulky [P666,14][PF<sub>6</sub>].</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"603 ","pages":"Article 113016"},"PeriodicalIF":2.4,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145555176","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 : 2025-11-14DOI: 10.1016/j.chemphys.2025.113028
Konok Chandro Roy , M. Riju Khandaker , M.N.H. Liton , M.M. Rahman , M.S.I. Sarker , M.K.R. Khan
Li2ZnSnO4, belongs to the quaternary (I2 − II − IV − O4) type of semiconductors. It is an essential candidate for solar cells and optoelectronic applications. In this study, our goal is to investigate the structural, electrical, and optical properties of Li2ZnSnO4. These properties are calculated using density functional theory (DFT), based on the first principles computational methods. The optimized lattice constants are found to be a = 5.46, b = 11.41, and c = 8.61 Å, with angle β = 129.0°. Li2ZnSnO4 compound demonstrates mechanical stability through its elastic tensor. It also exhibits soft, malleable, and highly machinable properties with poor elastic anisotropy. Two-dimensional and three-dimensional (2D and 3D) graphical visualizations are used to illustrate the elastic anisotropy. The material's stability is collectively ensured by its bond strength, Debye temperature, melting temperature, and Grüneisen parameter. Mülliken charge and bond analysis indicate a dominant ionic bonding character combined with covalent contributions. Li2ZnSnO4 exhibits a direct bandgap semiconductor with a bandgap energy of 2.01 eV. Various optical properties, such as dielectric response, absorption coefficient, reflectance, refractive index, photoconductivity, and energy loss characteristics have also been studied. The optical absorption coefficient is ∼105 cm−1 in the UV region. The low absorbance and reflectance of Li2ZnSnO4 compound in the infrared-to-visible region is a signature of transparent conducting oxide (TCO). Meeting redox potential conditions, Li2ZnSnO4 is considered as a promising photocatalyst for hydrogen generation and oxygen evolution.
Li2ZnSnO4，属于四元（I2−II−IV−O4）型半导体。它是太阳能电池和光电子应用的重要候选材料。在这项研究中，我们的目标是研究Li2ZnSnO4的结构、电学和光学性质。这些性质是利用密度泛函理论（DFT）计算的，基于第一性原理计算方法。优化后的晶格常数为a = 5.46, b = 11.41, c = 8.61 Å，角β = 129.0°。Li2ZnSnO4化合物通过弹性张量表现出力学稳定性。它还表现出柔软，延展性和高度可加工性能，弹性各向异性差。采用二维和三维（二维和三维）图形可视化来说明弹性各向异性。材料的稳定性由其结合强度、德拜温度、熔化温度和格力尼森参数共同保证。m lliken电荷和键分析表明，主要的离子键特征结合共价贡献。Li2ZnSnO4表现为直接带隙半导体，带隙能量为2.01 eV。各种光学性质，如介电响应、吸收系数、反射率、折射率、光电导率和能量损失特性也进行了研究。在紫外区光学吸收系数为~ 105 cm−1。Li2ZnSnO4化合物在红外-可见光区具有较低的吸光度和反射率，是透明导电氧化物（TCO）的特征。在满足氧化还原电位条件下，Li2ZnSnO4被认为是一种很有前途的产氢析氧光催化剂。
{"title":"First-principles investigation of structural, elastic, electronic, optical and photocatalytic properties of Li2ZnSnO4","authors":"Konok Chandro Roy , M. Riju Khandaker , M.N.H. Liton , M.M. Rahman , M.S.I. Sarker , M.K.R. Khan","doi":"10.1016/j.chemphys.2025.113028","DOIUrl":"10.1016/j.chemphys.2025.113028","url":null,"abstract":"<div><div>Li<sub>2</sub>ZnSnO<sub>4</sub>, belongs to the quaternary (I<sub>2</sub> − II − IV − O<sub>4</sub>) type of semiconductors. It is an essential candidate for solar cells and optoelectronic applications. In this study, our goal is to investigate the structural, electrical, and optical properties of Li<sub>2</sub>ZnSnO<sub>4</sub>. These properties are calculated using density functional theory (DFT), based on the first principles computational methods. The optimized lattice constants are found to be <em>a</em> = 5.46, <em>b</em> = 11.41, and <em>c</em> = 8.61 Å, with angle β = 129.0<sup>°</sup>. Li<sub>2</sub>ZnSnO<sub>4</sub> compound demonstrates mechanical stability through its elastic tensor. It also exhibits soft, malleable, and highly machinable properties with poor elastic anisotropy. Two-dimensional and three-dimensional (2D and 3D) graphical visualizations are used to illustrate the elastic anisotropy. The material's stability is collectively ensured by its bond strength, Debye temperature, melting temperature, and Grüneisen parameter. Mülliken charge and bond analysis indicate a dominant ionic bonding character combined with covalent contributions. Li<sub>2</sub>ZnSnO<sub>4</sub> exhibits a direct bandgap semiconductor with a bandgap energy of 2.01 eV. Various optical properties, such as dielectric response, absorption coefficient, reflectance, refractive index, photoconductivity, and energy loss characteristics have also been studied. The optical absorption coefficient is ∼10<sup>5</sup> cm<sup>−1</sup> in the UV region. The low absorbance and reflectance of Li<sub>2</sub>ZnSnO<sub>4</sub> compound in the infrared-to-visible region is a signature of transparent conducting oxide (TCO). Meeting redox potential conditions, Li<sub>2</sub>ZnSnO<sub>4</sub> is considered as a promising photocatalyst for hydrogen generation and oxygen evolution.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113028"},"PeriodicalIF":2.4,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576687","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 : 2025-11-14DOI: 10.1016/j.chemphys.2025.113029
I. Armenise , F. Esposito , G. Bonasia , G. Micca Longo , S. Longo
The application of multilayer feedforward backpropagation neural network is investigated for the implementation of state-to-state rate coefficients in a chemically reacting air system, which includes excited vibrational states and radicals. An oxygen dissociation reaction is chosen as a case study because of its importance, and also to compare it with a high-end traditional fit in terms of various performances in isolation and within a kinetic model. Different network architectures are experimented and compared, by varying the number of layers and neurons. The indications provided are relevant for practical use of different data implementation techniques in complex kinetic models.
{"title":"Evaluation of neural network in multivariate interpolation of rate coefficients in air kinetics","authors":"I. Armenise , F. Esposito , G. Bonasia , G. Micca Longo , S. Longo","doi":"10.1016/j.chemphys.2025.113029","DOIUrl":"10.1016/j.chemphys.2025.113029","url":null,"abstract":"<div><div>The application of multilayer feedforward backpropagation neural network is investigated for the implementation of state-to-state rate coefficients in a chemically reacting air system, which includes excited vibrational states and radicals. An oxygen dissociation reaction is chosen as a case study because of its importance, and also to compare it with a high-end traditional fit in terms of various performances in isolation and within a kinetic model. Different network architectures are experimented and compared, by varying the number of layers and neurons. The indications provided are relevant for practical use of different data implementation techniques in complex kinetic models.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113029"},"PeriodicalIF":2.4,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576688","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 : 2025-11-13DOI: 10.1016/j.chemphys.2025.113025
Carlos L. Di Prinzio , Luis N. Gerez , Esteban Druetta , Pastor I. Achával , Guillermo G. Aguirre Varela
The temporal evolution of the width of a scratch on the basal plane (0001) of a pure ice single crystal was analyzed under hydrostatic pressures of 0.1 MPa and 10 MPa. The sample was immersed in ultrapure silicone oil at −5 °C to suppress sublimation. A custom-designed pressurized cell enabled the application of controlled hydrostatic pressure, while time-lapse imaging was conducted using an optical microscope equipped with a digital camera. Images of the scratch were acquired at 30-min intervals over a 24-h period. Quantitative analysis of the scratch profiles was performed using image processing software, allowing for the extraction of the time-dependent broadening of the scratch under the specified hydrostatic pressures. From this, the surface self-diffusion coefficient was determined, providing insight into pressure-dependent surface mass transport mechanisms in ice.
{"title":"Surface self-diffusion of ice under high hydrostatic pressure","authors":"Carlos L. Di Prinzio , Luis N. Gerez , Esteban Druetta , Pastor I. Achával , Guillermo G. Aguirre Varela","doi":"10.1016/j.chemphys.2025.113025","DOIUrl":"10.1016/j.chemphys.2025.113025","url":null,"abstract":"<div><div>The temporal evolution of the width of a scratch on the basal plane (0001) of a pure ice single crystal was analyzed under hydrostatic pressures of 0.1 <em>MPa</em> and 10 <em>MPa</em>. The sample was immersed in ultrapure silicone oil at −5 <em>°C</em> to suppress sublimation. A custom-designed pressurized cell enabled the application of controlled hydrostatic pressure, while time-lapse imaging was conducted using an optical microscope equipped with a digital camera. Images of the scratch were acquired at 30-min intervals over a 24-h period. Quantitative analysis of the scratch profiles was performed using image processing software, allowing for the extraction of the time-dependent broadening of the scratch under the specified hydrostatic pressures. From this, the surface self-diffusion coefficient was determined, providing insight into pressure-dependent surface mass transport mechanisms in ice.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113025"},"PeriodicalIF":2.4,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576689","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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