Chemical Physics最新文献

{"title":"An electronic approach to understanding the kinetics of hydrogen peroxide formation","authors":"M.H. Ashurov ,&nbsp;B.L. Oksengendler ,&nbsp;N.N. Turaeva","doi":"10.1016/j.chemphys.2025.112794","DOIUrl":"10.1016/j.chemphys.2025.112794","url":null,"abstract":"<div><div>Hydrogen peroxide is an environmentally friendly oxidant that decomposes into water as its only byproduct. Various methods exist for its production, with direct synthesis standing out as a more sustainable and energy-efficient approach. This research introduces a kinetic model for the direct synthesis of hydrogen peroxide using catalysts, considering electron exchange between reaction intermediates and the catalyst. The model explains the size-dependent effects observed in Pd and Au nanocatalysts, offering insights for catalyst design in direct hydrogen peroxide synthesis. Furthermore, the electronic principles can be extended to the spontaneous formation of hydrogen peroxide at water/solid and air/droplet interfaces, shedding light on how the size of water microdroplets influences this process.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112794"},"PeriodicalIF":2.0,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144178688","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}

{"title":"Molecular dynamics simulations based on the diffusion interface of solid-phase Ti–Al system","authors":"Jianwei Zhang ,&nbsp;Qi Zhao ,&nbsp;Lei Zhang ,&nbsp;Jinyun Wang ,&nbsp;Cheng Sun","doi":"10.1016/j.chemphys.2025.112797","DOIUrl":"10.1016/j.chemphys.2025.112797","url":null,"abstract":"<div><div>The properties of Ti–Al alloys used in industrial applications, including their high-temperature stability and creep resistance, are primarily governed by diffusion processes. Most current studies on the interfacial diffusion of Ti–Al alloys utilize diffusion coupling techniques, which can only observe the interfacial diffusion properties at the microscopic level. Study focuses on modeling the diffusion process at the Ti–Al interface using molecular dynamics to elucidate the atomic-scale mechanism of interfacial diffusion, thereby facilitating a comprehensive understanding of diffusion and allowing the simulation to be conducted in a controlled manner. The simulation results indicate that the square of the diffusion region's thickness is proportional to time. The calculation results show that the Ti(100)//Al(0001) interface has a higher propensity for interdiffusion compared to the Ti(110)//Al(0001) interface. Moreover, the interdiffusion between Ti and Al leads to the amorphization of the Ti–Al interfacial region. The formation of TiAl₃ in the diffusion region was confirmed.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112797"},"PeriodicalIF":2.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144170353","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}

{"title":"Investigating nitrogen molecule adsorption on borophene surface using reactive molecular dynamics simulation","authors":"Mahnaz Sababkar,&nbsp;Masumeh Foroutan","doi":"10.1016/j.chemphys.2025.112795","DOIUrl":"10.1016/j.chemphys.2025.112795","url":null,"abstract":"<div><div>This study explores the chemical adsorption mechanism of nitrogen molecules on the borophene surface at temperatures of 300 K, 500 K, 700 K, and 900 K. The adsorption process consists of three steps. Initially, a bond forms between a nitrogen atom and a boron atom. Subsequently, the angle between the nitrogen molecule and the boron atom changes, leading to various potential energy states and transition states. Finally, a second bond forms with another nitrogen atom, occurring after a key transition state where multiple bonds exist. By analyzing potential energy changes, and atomic distances, we elucidate the adsorption mechanism and atomic placements during transition states. To the best of our knowledge, this is the first theoretical investigation of N₂ adsorption on a borophene surface. Moreover, our findings reveal a temperature-dependent reaction pathway, with distinct adsorption mechanisms observed at higher temperatures. Notably, the mechanism evolves with temperature, revealing that products formed at 900 K are more stable.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112795"},"PeriodicalIF":2.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144170476","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}

{"title":"ZnI2/SnS2 van der Waals heterojunction: A high-efficiency direct Z-type photocatalyst for overall water-splitting predicted from first-principles calculation","authors":"Yan Zhang,&nbsp;Shu-Zhuan Sun,&nbsp;Li Duan","doi":"10.1016/j.chemphys.2025.112796","DOIUrl":"10.1016/j.chemphys.2025.112796","url":null,"abstract":"<div><div>The structural, electronic, optical and photocatalytic characteristics of ZnI₂/SnS₂ heterojunction have been investigated utilizing first-principles calculation. The ZnI₂/SnS₂ heterojunction is an indirect bandgap (2.08 eV) semiconductor with type-II energy band arrangement, facilitating the separation of photogenerated carriers and improving the utilization of solar energy. The charge transfer from ZnI₂ layer to SnS₂ layer is 0.031 |e| and forms a built-in electric field, which accelerates the separation of photogenerated carriers. The ZnI₂/SnS₂ heterojunction has excellent optical properties in the visible light range with a solar-to‑hydrogen conversion efficiency of 28.7 %. The applied biaxial strain can effectively modulate the electronic structure of the ZnI₂/SnS₂ heterojunction. The O₂ evolution half reaction is always taken place in the biaxial strain range from −6 % to 6 % and any pH values. While the H₂ evolution half reaction can be taken place in the biaxial strain range from −6 % to 6 % in acidic environment.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112796"},"PeriodicalIF":2.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144178686","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}

{"title":"Vibrational dynamics in solid methanol investigated through inelastic neutron scattering and molecular dynamics simulations","authors":"Daniele Colognesi ,&nbsp;Simone De Panfilis ,&nbsp;Ferdinando Formisano ,&nbsp;Miguel Ángel González ,&nbsp;Svemir Rudić ,&nbsp;Alberto Santonocito","doi":"10.1016/j.chemphys.2025.112773","DOIUrl":"10.1016/j.chemphys.2025.112773","url":null,"abstract":"<div><div>The vibrational dynamics of crystalline <span><math><mi>α</mi></math></span>-phase methanol and its three isotopic substitutes has been investigated by inelastic neutron scattering, classical molecular dynamics, and <em>ab initio</em> lattice dynamics. Experimental data were collected on the TOSCA neutron spectrometer at low temperature (<span><math><mrow><mi>T</mi><mo>≤</mo><mn>15</mn></mrow></math></span> K). Classical molecular dynamics trajectories were obtained using a modified OPLS-AA effective force field. <em>Ab initio</em> lattice dynamics simulations were performed in the DFT framework using a high-level hybrid functional. Methanol vibrational bands have been divided into two main intervals: “external” (i.e., including lattice phonons and molecular librations) and intramolecular. The former domain showed a large dispersion of the vibrational excitations and, in the case of CH<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>OH and CH<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>OD, high-resolution H-projected vibrational densities of states have been obtained. Such physical quantities favorably compared with the respective infrared/Raman data, while only a semi-quantitative agreement with simulated spectra has been achieved. Above 200 meV, large multiphonon components in the experimental data masked all the weak fundamental vibrational bands. Still, in spite of these difficulties, the reconstruction of the intramolecular methanol spectra has been attempted producing globally good results for CH<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>OH and CH<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>OD, while those pertaining to CD<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>OH and CD<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>OD included small discrepancies in the band positions and intensities. DFT lattice dynamics calculations compare reasonably well with the neutron scattering spectra, but still worse than what classical molecular dynamics simulations do. We underline the importance of the present results for interpreting spectral data of amorphous water-methanol mixtures.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112773"},"PeriodicalIF":2.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144170351","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}

{"title":"Theoretical study on the effect of H2O and ionic liquid on CO2 reduction on Cu surface","authors":"Zhiqi Zhang ,&nbsp;Jingli Han ,&nbsp;Yongpeng Yang","doi":"10.1016/j.chemphys.2025.112792","DOIUrl":"10.1016/j.chemphys.2025.112792","url":null,"abstract":"<div><div>Electrolyte plays a vital role in the CO₂ reduction on metal surface. The aqueous solutions of ionic liquids (ILs) as electrolytes have been demonstrated to be more efficient for CO₂ reduction compared to pure ionic liquid. We investigated the effect of H₂O and ILs ([Emim][PF₆], [Pmim][PF₆] and [Bmim][PF₆]) on CO₂ activation on Cu surface. CO₂ prefers to interact with ILs by cation alkyl and anion, and the interaction is stronger than that between CO₂ and H₂O. On Cu surfaces, the physical adsorption energy of CO₂ co-adsorbed with H₂O is close to that co-adsorbed with ILs due to the change of interaction pattern of CO₂ with ILs. H₂O and ILs can both be beneficial to the CO₂ reduction. However, H₂O plays more important for CO₂ activated adsorption and reduction reaction. ILs can significantly enhance the solubility of CO₂ in electrolyte.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112792"},"PeriodicalIF":2.0,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144170354","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}

{"title":"Theoretical calculation of single-atom supported BN catalyzing CO2 hydrogenation to formic acid: A first principles study","authors":"Naimatullah ,&nbsp;Yuanyuan Cui ,&nbsp;Qinqin Yuan ,&nbsp;Longjiu Cheng","doi":"10.1016/j.chemphys.2025.112781","DOIUrl":"10.1016/j.chemphys.2025.112781","url":null,"abstract":"<div><div>Exploring suitable catalysts for CO₂ hydrogenation is crucial to alleviate greenhouse effect and produce useful chemicals. In this work, the potential of a single transition metal atom embedded in a boron nitride monolayer (TM-BN) as a catalyst for CO₂ hydrogenation to formic acid was evaluated using first-principles calculations. The TM-BN systems (TM = Sc, Ti, V, Cr and Mn) exhibit significant stability due to the strongly interaction between the TM-3d orbitals and the 2p orbitals of the three surrounding N atoms. While, only V-BN system shows the strongest adsorption energies of CO₂ and H₂ than others. Four mechanisms were proposed for CO₂ hydrogenation to formic acid, where the process including CO₂ absorbed on V-BN monolayer in side-on type as initial state has the lowest energy barriers of 0.44 eV. This work not only provides a new way for CO₂ hydrogenation but also further broadens the range of applications for BN-based materials.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112781"},"PeriodicalIF":2.0,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154544","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}

{"title":"Cross sections for scattering of excited argon atoms on helium atom","authors":"A. Pershin ,&nbsp;S. Miroshnichenko ,&nbsp;A. Palov","doi":"10.1016/j.chemphys.2025.112770","DOIUrl":"10.1016/j.chemphys.2025.112770","url":null,"abstract":"<div><div>The objective of this study was to obtain elastic and inelastic cross sections for the excited Ar atom on He in the ground state from calculated potential energy curves and nondiagonal matrix elements. The calculations of potential energy curves, spin–orbit interactions, and nonadiabatic coupling matrix elements were carried out using the MOLPRO 2015 electronic structure program for a total of 49 spin–orbit states. On their base inelastic scattering cross sections were calculated using the exponential Born distorted wave approach (EBDW). The calculated cross sections and rate constants for inelastic processes can be employed in the calculation of dynamics nonradiative transitions.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112770"},"PeriodicalIF":2.0,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144125305","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}

{"title":"Design and performance study of nitrogen-containing cuneane derivatives","authors":"Dongrun Tang ,&nbsp;Yunlu Li ,&nbsp;Xuan Zhang ,&nbsp;Mei Xue ,&nbsp;Jianlong Wang ,&nbsp;Lizhen Chen","doi":"10.1016/j.chemphys.2025.112779","DOIUrl":"10.1016/j.chemphys.2025.112779","url":null,"abstract":"<div><div>This study introduces nitrogen atoms into the cuneane based on the structural characteristics of <em>β</em>-HMX and <em>ε</em>-CL-20, forming a nitrogen-containing cuneane (CuneaneN) core structure. The compounds CuN-1 to CuN-8 are then designed by modifying the structure with -NO₂ groups. The molecular structure, crystal density, oxygen balance, enthalpy of formation, detonation performance, and safety of these compounds are evaluated using density functional theory (DFT). The results show that as the number of nitro groups increases, the crystal density and enthalpy of formation gradually increase, while the oxygen balance initially increases and then decreases, which affects the detonation performance. Furthermore, the calculations reveal that as the number of nitro groups increases, the sensitization effect within the molecules strengthens, leading to an increase in impact sensitivity and a decrease in thermal stability. Among these compounds, CuN-5 exhibits the best performance (<em>ρ</em> = 1.93 g<span><math><mo>·</mo></math></span>cm^-³, <em>Q</em> = 1690.47 cal<span><math><mo>·</mo></math></span>g^-1, <em>D</em> = 9.49 km<span><math><mo>·</mo></math></span>s^-1, <em>p</em> = 42.47 GPa, BDE of N-NO₂ = 183.94 kJ<span><math><mo>·</mo></math></span>mol^-1, BDE of C-NO₂ = 279.42 kJ<span><math><mo>·</mo></math></span>mol^-1, <em>h</em>₅₀ = 9.55 cm). These findings indicate that the construction of nitrogen-containing cage molecules, combined with the modification of energetic groups, can lead to the design of high-energy-density materials with excellent performance and good safety.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112779"},"PeriodicalIF":2.0,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137940","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}

{"title":"Influences of secondary and tertiary amines in epoxy resins on water dynamics by all-atomic molecular dynamics simulations","authors":"Yuji Higuchi ,&nbsp;Yasuyuki Nakamura ,&nbsp;Masanobu Naito ,&nbsp;Yoshihisa Fujii","doi":"10.1016/j.chemphys.2025.112766","DOIUrl":"10.1016/j.chemphys.2025.112766","url":null,"abstract":"<div><div>All-atomic molecular dynamics simulations were conducted to elucidate the water dynamics around amines in epoxy resins. The rotational relaxation and translational diffusion of water molecules were slow in an epoxy resin based on a secondary amine, compared with those in one based on a tertiary amine. This qualitatively agrees with experimental quasielastic neutron scattering results, demonstrating the validity of the simulations. For the tertiary amine, water cluster formation accelerated the rotational relaxation of water, while the secondary amines attracted water molecules slightly more strongly than tertiary amines, preventing water from forming large clusters and slowing down translational diffusion.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112766"},"PeriodicalIF":2.0,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144115417","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}