Physical Chemistry Chemical Physics最新文献

{"title":"Metal intercalation-induced magnetic modulation in VS2 bilayer: a first principles study","authors":"Dantong Li, Xiaocheng Zhou, Yu Wang, Yafei Li","doi":"10.1039/d5cp00869g","DOIUrl":"https://doi.org/10.1039/d5cp00869g","url":null,"abstract":"Two-dimensional (2D) magnetic materials have emerged as highly promising candidates for spintronic applications owing to their unique properties. However, they tend to exhibit antiferromagnetic coupling when stacked, which limits their broader applications. It would be of critical importance to manipulate the magnetic coupling and exploring their applications in low-energy-consumption spintronic devices. Here, we theoretically investigated the electronic and magnetic properties of VS2 bilayer with intercalated transition metals (TMs) based on density functional theory (DFT) computations and nonequilibrium Green’s function (NEGF) method. It is revealed that metal intercalation can significantly enhance the ferromagnetic exchange interaction. The TM-intercalated VS2 bilayers (TM-VS2) exhibit diverse electronic and magnetic properties, which can be precisely tuned via controlling the type and concentration of intercalated metals. The spin-polarized transport calculations demonstrate that the TM-VS2 bilayer with half-metallicity exhibits a pronounced spin filtering property. Our theoretical study provides a promising route to design and modulate the magnetic properties of 2D ferromagnets for their applications in advanced spintronic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"103 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745325","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":"Ultrafast X-ray induced damage and nonthermal melting in cadmium sulfide","authors":"Nikita Medvedev, Aldo Artímez-Peña","doi":"10.1039/d5cp00525f","DOIUrl":"https://doi.org/10.1039/d5cp00525f","url":null,"abstract":"Cadmium sulfide is a valuable material for solar cells, photovoltaic, and radiation detectors. It is thus important to evaluate the material damage mechanisms and damage threshold in response to irradiation. Here, we simulate the ultrafast XUV/X-ray irradiation of CdS with the combined model, XTANT-3. It accounts for nonequilibrium electronic and atomic dynamics, nonadiabatic coupling between the two systems, nonthermal melting and bond breaking due to electronic excitation. We find that the two phases of CdS, zinc blende and wurtzite, demonstrate very close damage threshold dose of ~0.4-0.5 eV/atom. The damage is mainly thermal, whereas with increase of the dose, nonthermal effects begin to dominate leading to nonthermal melting. The transient disordered state is a high-density liquid, which may be semiconducting or metallic depending on the dose. Later recrystallization may recover the material back to the crystalline phase, or at high doses create an amorphous phase with variable bandgap. The revealed effects may potentially allow for controllable tuning of the band gap via laser irradiation of CdS.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"58 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737266","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":"Advances in Single-Molecule Electrical Transport Studies of Peptides","authors":"Cunxin Han, Chao Chen, Hanqing Shi, Wenzhe Chen, Wei Sun, Bing Li","doi":"10.1039/d5cp00128e","DOIUrl":"https://doi.org/10.1039/d5cp00128e","url":null,"abstract":"The charge transport between peptide molecules is one of the crucial factors sustaining various biochemical processes within biological organisms. Understanding the charge transport processes between peptide molecules is of great significance for further investigating life reaction processes. Through single-molecule electronics characterization techniques, we have reviewed the effects of the structure of peptide molecules and external experimental factors on their charge transport. Additionally, we have summarized the latest research on supramolecular interactions between peptide chains, particularly focusing on the even-odd effect. This not only enhances our understanding of the charge transport mechanisms between peptide molecules but lays a solid theoretical foundation for the widespread application of peptide molecules in fields such as biological devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"40 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737270","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":"Ultrafast pre-solvated dodecane hole capture and subsequent damage of used nuclear fuel extraction ligands DEHBA, DEHiBA, HONTA, CMPO, HEH[EHP] and TBP","authors":"Andrew R. Cook, Rupali G Deokar","doi":"10.1039/d5cp00914f","DOIUrl":"https://doi.org/10.1039/d5cp00914f","url":null,"abstract":"Two classes of used nuclear fuel (UNF) extraction ligands, amide (DEHBA, DEHiBA, HONTA) and organophosphorus (CMPO, HEH[EHP], TBP), were selected to study radiation induced damage at picosecond to nanosecond timescale using electron pulse radiolysis in n-dodecane (DD) and supported by quantum chemical calculations. Spectra after radiolysis of 200 mM extraction ligands were recorded in DD/0.3 M DCM. Absorption peaks at 365, 365, 400 and 387 nm in case of DEHBA, DEHiBA, HONTA and CMPO respectively are assigned to triplet excited states. Additional absorption peaks at 420, 460 and 600 nm of DEHBA, DEHiBA and HONTA respectively were identified as due to ligand radical cations. A concentration dependent absorption peak at 600 nm in the case of CMPO was observed and assigned due to a combination of CMPO●+, (CMPO)2●+ and possibly a radical degradation product of CMPO. Weak absorption peaks at 650 and 550 nm in case of HEH[EHP] and TBP were observed and tentatively assigned to their radical cations. A two-component DD●+ decay in the presence of ligands was observed due to different ligand oxidation mechanisms: ultrafast capture of pre-solvated DD holes and diffusive capture of solvated DD holes. At high extraction ligand concentrations (> 100 mM), the majority of DDholes were captured via an ultrafast pre-solvated pathway in < 10 ps with C37 values of 389, 401, 270, 374, 458 and 340 mM for DEHBA, DEHiBA, HONTA, CMPO, HEH[EHP] and TBP respectively. Following ultrafast capture, the remainder of DD holes became solvated and were captured with k = (2.32 ± 0.13), (1.78 ± 0.12), (1.38 ± 0.2), (0.98 ± 0.081), (1.09 ± 0.08) and (1.77 ± 0.046) x 1010 for DEHBA, DEHiBA, HONTA, CMPO, HEH[EHP] and TBP respectively. Subsequent hole transfer from the extraction ligands●+ to the low IP solute tri‐p‐tolylamine (TTA) showed only 4-16% hole transfer most likely indicating ligand●+ degradation in 0.9-4.6 ns.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"13 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745392","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":"Understanding the hydrocarbon - PFSA ionomer conductivity gap in hydrogen fuel cells","authors":"William Bangay, Michael Yandrasits, Wayne Hayes","doi":"10.1039/d5cp00334b","DOIUrl":"https://doi.org/10.1039/d5cp00334b","url":null,"abstract":"Hydrocarbon ionomers (HCs) have the potential to replace perfluorinated sulfonic acids (PFSAs), which are currently used in electrolyser or fuel cell membranes. To be a truly viable alternative, HCs must have conductivity across the operating range and cell lifetime comparable to PFSAs. Conductivity is an important property of membranes because it affects the energy efficiency of a fuel cell or electrolyser. By examining conductivity as a function of water volume fraction, it becomes evident that HC ionomers have consistently lower conductivity at low relative humidity. To better understand this ’conductivity gap’, conductivity was converted to proton diffusivity and analysed using General Effective Media (GEM) theory for the first time. This analysis revealed that all ionomers require similar hydration levels for proton dissociation, and proton diffusion coefficients in the dry polymer are responsible for the conductivity gap. It is suggested that the membrane tortuosity ultimately accounts for the dry membrane’s proton diffusivity and low RH conductivity. As the membrane hydrates however, all ionomers exhibit similar diffusion coefficients, indicating that conductivity at high humidity is limited by proton concentration.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"31 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737230","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":"Controlled release mechanism of drugs from onion-like dendrimersomes: insight from dissipative particle dynamics simulation","authors":"Shenghong Guo, Xiangkun Yu, You-Liang Zhu, Li-Li Zhang, Yi-Neng Huang","doi":"10.1039/d4cp04780j","DOIUrl":"https://doi.org/10.1039/d4cp04780j","url":null,"abstract":"Compared with current lipid nanoparticle delivery system, a new drug delivery system that can simultaneously achieve the high stability for temperature and time, and the controllable release of drugs, will be smart and next-generation. However, designing such system for complex human body environment remains a daunting challenge. Herein, we use highly stable multilayer dendrimersomes as a model to study the mechanism of controlled release of drugs through stimulus-response by dissipative particle dynamics simulations. The results show that when the dendrimersomes remain intact, the release of encapsulated hydrophilic, hydrophobic, and neutral drugs is minimal. Once the amphiphilic dendrimers in the dendrimersomes are decomposed beyond a threshold by cleaving the linkers connecting hydrophobic and hydrophilic segments, which can be achieved by exogenous perturbations, a significant or complete release of the drugs occurs. The introduction of liquid flow will remarkably enhance the release capability of drugs in decomposed dendrimersomes. These insights into the controlled release of drugs at microscopic view offer helpful guidance for the development of advanced drug delivery vehicles.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"36 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737232","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":"Oxygen exchange kinetics of BaGd0.3La0.7Co2O6−δ with exsolved Co3O4 nanoparticles in dry and humid atmospheres","authors":"Jónína Björg Guðmundsdóttir, Vincent Thoreton, Bo Jiang, Anuj Pokle, Einar Vøllestad, Reidar Haugsrud, Jonathan Marc Polfus","doi":"10.1039/d4cp04791e","DOIUrl":"https://doi.org/10.1039/d4cp04791e","url":null,"abstract":"The oxygen exchange kinetics of BaGd0.3La0.7Co2O6−δ (BGLC37) were investigated with pulsed isotope exchange (PIE) measurements in dry and humid atmospheres in the temperature range 400–600°C in 0.005-0.21 bar O2. Synchrotron X-ray diffraction and scanning transmission electron microscopy (STEM) revealed exsolved Co3O4 nanoparticles dispersed on the surfaces that may contribute to the catalytic activity of the material towards the oxygen exchange reactions. The obtained oxygen exchange rate was 4.45×10−3 mol m−2 s−1 at 600°C in 0.21 bar O2 with an activation energy of 0.84 eV. The rate determining step of the exchange reaction was determined to be dissociative adsorption of oxygen in both dry and humid atmospheres based on the individual rates of dissociative adsorption and incorporation, as well as a pO2 dependencies of the overall exchange rate of around 1. The effect of water on the overall exchange rate was found to be dependent on the oxygen partial pressure, decreasing the rate at 0.21 bar O2 and 600°C by a factor of approx. 2, while increasing the rate at 0.02 bar and 0.005 bar O2 by a similar amount. In situ thermogravimetric analysis was used to characterise the oxygen non-stoichiometry of the material throughout the oxygen exchange measurements.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"72 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737265","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":"Correction: Isomerisation of phosphabutyne and a photochemical route to phosphabutadiyne (HC3P), a phosphorus analogue of cyanoacetylene","authors":"Arun-Libertsen Lawzer, Elavenil Ganesan, Thomas Custer, Jean-Claude Guillemin, Robert Kołos","doi":"10.1039/d5cp90069g","DOIUrl":"https://doi.org/10.1039/d5cp90069g","url":null,"abstract":"Correction for ‘Isomerisation of phosphabutyne and a photochemical route to phosphabutadiyne (HC<small>₃</small>P), a phosphorus analogue of cyanoacetylene’ by Arun-Libertsen Lawzer <em>et al.</em>, <em>Phys. Chem. Chem. Phys.</em>, 2025, https://doi.org/10.1039/d4cp04182h.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"16 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737267","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":"Getting Insights into the Edge Effect of FeN4C Catalysts on the Electroreduction of CO to Methane by Density Functional Theory Calculations","authors":"Yuxin Xie, Di Li, Hongjing Dai, Xiaohua Chen","doi":"10.1039/d5cp00495k","DOIUrl":"https://doi.org/10.1039/d5cp00495k","url":null,"abstract":"Isolated FeN<small>₄</small> atomically dispersed on graphene (FeN<small>₄</small>C) is burgeoning as versatile catalysts for electrochemical carbon monoxide reduction reaction (CORR). However, the impact of the local coordination environment of FeN<small>₄</small> on CORR performance is still lack of underlying understanding, particularly the intrinsic activity differences among various FeN<small>₄</small> sites. Herein, by using density functional theory, we investigated the electrocatalytic performance of FeN<small>₄</small> embedded in the interior, armchair- and zigzag-edge of carbon sheet for converting CO to valuable C1 products. The Gibbs free energy profile analyses along the possible reaction pathways identify that the armchair-edge FeN<small>₄</small> site (FeN<small>₄</small>@A) exhibits the best catalytic activity and the highest CH<small>₄</small>-slectivity through the *CHO key intermediate with the lowest free energy change of 0.31 eV. The corresponding kinetic analyses also confirm that FeN<small>₄</small>@A possesses the fastest kinetic CORR activity with an activation barrier of 1.31 eV for the rate-determining step. In addition, the d-band center calculations suggest that the local environment of FeN<small>₄</small> site can regulate the overlap of the d-orbitals of the center Fe and the p-orbitals of coordination N atoms to change the position of d-band center relative to the Fermi level, which significantly affects the catalytic activity of FeN<small>₄</small> site. The d-band center of FeN<small>₄</small>@A is very close to the Fermi level in energy, indicating that the armchair-edge of graphene favors the FeN<small>₄</small> site to achieve the high CORR performance. These results provide insight into the relationship of electronic structure-catalytic activity of different-type FeN<small>₄</small>C catalysts, which may guide the design of novel electrode materials with improved performances for achieving efficient multi-intermediate electrocatalysis.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737264","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":"Evaluating and interpreting the exchange correlation contributions to the total static and interelectron interaction force densities, with a force-field perspective on the exchange charge density","authors":"Sergey V. Kartashov, Robert R. R. Fayzullin","doi":"10.1039/d5cp00061k","DOIUrl":"https://doi.org/10.1039/d5cp00061k","url":null,"abstract":"A crucial aspect of the conservative exchange force <strong>F</strong><em><small>_x</small></em>(<strong>r</strong>) is the possible existence of nonnuclear basins in the corresponding vector field, which encompass internuclear binding regions for various covalent bonds. The intricate behavior of <strong>F</strong><em><small>_x</small></em>(<strong>r</strong>) can be evaluated through its component contributions to the total static force density <em>F</em>(<strong>r</strong>) and the interelectron interaction force density <strong>F</strong><small>_ee</small>(<strong>r</strong>). The sought-after contributions are expressed as the scalar projection of the partial force (SPPF) onto the corresponding cumulative force. The resulting scalar component distribution permits the differentiation of the regions of physical space, exhibiting directional divergence or convergence between the two considered force fields. The scalar projections of <strong>F</strong><em><small>_x</small></em>(<strong>r</strong>) onto <em>F</em>(<strong>r</strong>) and <strong>F</strong><small>_ee</small>(<strong>r</strong>) enable the identification of shared electrons and lone electron pairs. Concurrently, the SPPF discloses the counteracting mechanism for the charge-transfer-induced quantum chemical response, which is implicated in a negative contribution of <strong>F</strong><em><small>_x</small></em>(<strong>r</strong>) to <em>F</em>(<strong>r</strong>) for the interatomic transferred density. Furthermore, <strong>F</strong><em><small>_x</small></em>(<strong>r</strong>) typically positively contributes to <strong>F</strong><small>_ee</small>(<strong>r</strong>) within a part of each binding region, thereby facilitating the retention of electron “glue” between nuclei. These findings demonstrate the mechanical role of the exchange correlation in chemical bonding and the interatomic electron transfer in many-electron multinuclear systems. Additionally, the exchange charge density <strong>F</strong><em><small>_x</small></em>(<strong>r</strong>)/(4π), which signifies the effective electron density distribution that arises from the influence of <strong>F</strong><em><small>_x</small></em>(<strong>r</strong>), has been shown to accurately reproduce the details of subatomic structure, with negative values indicating electron cloud thickening. The underlying procedures are readily implementable and offer reliable chemical structure descriptors.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"102 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737269","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}