Chemical Physics最新文献

{"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":"Adsorption of lithium ions from liquid resources by dual surfactant rod mesoporous composite lithium-ion sieve PVB-HTO-1","authors":"Mengyu Lin ,&nbsp;Jiumei Chu ,&nbsp;Dianjun Dong ,&nbsp;Xue Yang ,&nbsp;Dianquan Dong","doi":"10.1016/j.chemphys.2025.112793","DOIUrl":"10.1016/j.chemphys.2025.112793","url":null,"abstract":"<div><div>Spinel-type titanium-based lithium-ion sieve H₄Ti₅O₁₂ has excellent theoretical adsorption capacity and selectivity. Still, spinel-type lithium adsorbents prepared in existing studies have poor adsorption, poor recyclability, and difficulty in recovery. To solve the above problems, composite mesoporous ion sieves, Polyvinyl Butyral-H₄Ti₅O₁₂–1 (PVB-HTO-1) modified with dual surfactants, were synthesized for the first time in this paper. Hydrophilic lithium-ion sieve HTO-1 with a mesoporous structure was synthesized by adding two surfactants, CTAB and F127. Then the modified ion sieve was composited with PVB to make a fine rod-like composite material, PVB-HTO-1, with a diameter of no more than 0.5 mm, to solve the limitation of the industrial application that the recycling of powdered ion sieve is difficult. The bi-component surfactant-derived ion sieve, PVB-HTO-1, exhibits superior hydrophilicity and possesses a porous mesoporous framework that facilitates ion exchange processes, achieving adsorption equilibrium within a timeframe of three hours. It demonstrates a remarkable maximum adsorption capacity of 53.25 mg/g. Even after undergoing five cycles of adsorption and desorption, the material's adsorption capacity remains at over 90 % of its initial value, indicative of its robust cyclic stability. The uptake of Li⁺ ions by PVB-HTO-1 aligns with the pseudo-second-order kinetic model and conforms to the Langmuir isothermal adsorption model.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112793"},"PeriodicalIF":2.0,"publicationDate":"2025-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144262364","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}

{"title":"Investigation on optical illumination effect on transport properties and resistive switching of poly crystalline BiFeO3/ITO heterojunction","authors":"H.K. Rathod ,&nbsp;Davit Dhruv ,&nbsp;M.V. Kanani ,&nbsp;Alpa Zankat ,&nbsp;R.K. Trivedi ,&nbsp;A.D. Joshi ,&nbsp;P.S. Solanki ,&nbsp;N.A. Shah","doi":"10.1016/j.chemphys.2025.112782","DOIUrl":"10.1016/j.chemphys.2025.112782","url":null,"abstract":"<div><div>In the present studies we reported the optical modulation of charge transport and resistive switching behavior in polycrystalline BiFeO₃ thin film deposited ITO coated glass substrate via the chemical solution deposition technique. Structural analysis using grazing angle incidence X-ray diffraction (GIXRD) confirms the formation of polycrystalline BiFeO3 phase. The current-voltage characteristics were measured under both dark and illuminated conditions (White light LED 450–470 nm Philips LUXEON 3030 2D) in a current perpendicular to plane (CPP) configuration with Ag as top electrode and ITO as bottom electrode at room temperature .Optical illumination significantly enhanced the current response,notably at +1 V suggesting efficient photoinduced carrier generation and transport .Resistive switching, investigated under cyclic bias of 0 V → +2 V → 0 V → -2 V → 0 V,exhibited notable improvement in switching performance under illumination. Charge transport analysis indicates that the conduction is governed by space charge limited current (SCLC) mechanism under both dark and light conditions. These findings demonstrate a strong correlation between optical excitation and resistive switching in BiFeO3 films, providing insights into the design of photo assisted nonvolatile memory elements and light responsive oxide electronics.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112782"},"PeriodicalIF":2.0,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144125309","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":"Investigation on the effect of surface orientations on helium behavior using first-principles","authors":"ShuLong Wen ,&nbsp;Min Pan ,&nbsp;XiangYang Wang ,&nbsp;HuiQiu Deng","doi":"10.1016/j.chemphys.2025.112783","DOIUrl":"10.1016/j.chemphys.2025.112783","url":null,"abstract":"<div><div>The structure and stability of the Y₂O₃ surface, along with helium (He) behavior near the surface, were investigated using first-principles calculations. Surface energy, dissolution, diffusion, and clustering behaviors were analyzed to explore He bubble nucleation mechanisms. Among the studied surface models, the O-Ter termination of the Y₂O₃ (1 1 1) surface demonstrated the highest stability due to its stoichiometric structure. Dissolution and diffusion analyses revealed that He is most stable at the (4 2 2) surface but is more readily released near the (1 0 0) surface under irradiation. Multi-He cluster configurations near the (1 1 1) surface indicated that a low-dissolution energy region can accommodate up to five He atoms before forming a nucleation center. These clusters initially grow parallel to the surface and later extend perpendicularly, ultimately forming He bubbles. The results provide critical insights into He behavior near Y₂O₃ surfaces in ODS-W materials.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112783"},"PeriodicalIF":2.0,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144125307","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":"Influence of electrodes in enhancing the thermoelectric performance of Mn-Cn-Mn (n = 7) molecular chain","authors":"Shankar Prasad Mitra ,&nbsp;Partha Sarkar ,&nbsp;Ajit Biswas ,&nbsp;Dipankar Adak ,&nbsp;Sabyasachi Sen","doi":"10.1016/j.chemphys.2025.112772","DOIUrl":"10.1016/j.chemphys.2025.112772","url":null,"abstract":"<div><div>The present study enlightens an in-depth investigation into the comparative analysis of thermoelectric performance between <em>g</em>-<span><math><msub><mi>C</mi><mn>4</mn></msub><msub><mi>N</mi><mn>3</mn></msub></math></span>and graphene electrodes with a molecular chain of Mn-C_n-Mn (<span><math><mi>n</mi><mo>=</mo><mn>7</mn></math></span>), a one-dimensional (1-D) thermoelectric system as the molecular channel. The study explores the critical factors influencing the figure of merit (ZT) and the overall thermoelectric behaviour of these systems. Results demonstrate that at lower temperatures an efficient thermoelectric device with high ZT is obtained with <em>g</em>-<span><math><msub><mi>C</mi><mn>4</mn></msub><msub><mi>N</mi><mn>3</mn></msub><mspace></mspace></math></span>electrodes; however, the same is not maintained above 225 K; instead, better and consistent thermoelectric performance at higher temperatures is obtained with Graphene electrodes. Our study therefore highlights the crucial role of the choice of electrodes in deciding final thermoelectric performance. The thermoelectric performance is analysed through the system's temperature dependence of the Seebeck coefficient, electrical conductance, and thermal conductance. It is observed that temperature dependence of Seebeck coefficient (<em>S</em>) has a direct impact on ZT variation. The high thermal conductivity (<em>k</em>) along with low S of graphene electrode is responsible for relatively lower ZT despite large higher electrical conductivity (<span><math><msub><mi>G</mi><mi>e</mi></msub><mo>)</mo><mo>.</mo></math></span>Throughout the range of temperature variation, the electronic part of thermal conductivity (<em>k</em>) is found to be weaker than the phononic part in both systems.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"597 ","pages":"Article 112772"},"PeriodicalIF":2.0,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144125306","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}