Physical Chemistry Chemical Physics最新文献

{"title":"B/N modified GDY as a rare base 2D sensor: a first-principles study","authors":"Ruiying Zhang, Xia Zeng, Lin Yu, Lingyu Meng, Wenjin Miao, Lingxia Jin","doi":"10.1039/d5cp00209e","DOIUrl":"https://doi.org/10.1039/d5cp00209e","url":null,"abstract":"Detecting DNA rare bases is essential for diagnosing genetic disorders and cancers. However, their low abundance and high structural similarity make selective and sensitive detection challenging. The two-dimensional functionalized carbon material graphdiyne (GDY) holds great promise for enhancing sensor performance due to its excellent electronic properties, biocompatibility, and ease of functionalization. This study employs density functional theory (DFT) to investigate the adsorption behavior of rare bases on GDY and R-GDY (R = B/N) surfaces. Essential factors, including adsorption energy, bandgap, charge transfer, and density of states, are systematically analyzed. Additionally, critical sensor performance metrics, such as deposition time, sensitivity, and selectivity are predicted, providing valuable insights into the potential applications of these materials. The results indicate that while pure GDY can specifically recognize 5-hydroxymethylcytosine, its sensitivity is limited. In contrast, R-GDY stably adsorbs rare bases <em>via</em> π–π interactions, exhibiting good reversibility and moderate charge transfer, which significantly enhance its sensitivity. R-GDY effectively distinguishes between rare bases based on translocation time, making it ideal for the development of efficient and reusable electrochemical biosensors, thus providing a reliable approach for clinical diagnostics.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"72 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745322","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":"High performance photocatalytic water splitting in two-dimensional BN/Janus SnSSe heterojunctions: ab initio study","authors":"Fan Xiang, RuiHao Tan, QingYu Xie, KaiWang Zhang","doi":"10.1039/d5cp00614g","DOIUrl":"https://doi.org/10.1039/d5cp00614g","url":null,"abstract":"Designing and exploring a photocatalyst with interfacial electric fields for hydrogen production <em>via</em> water splitting is a critical area of research. To achieve efficient hydrolysis reactions, heterojunction materials have garnered significant attention due to their excellent electronic structures and interfacial properties. In this study, we designed a 2D BN/SnSSe heterojunction and investigated its photovoltaic properties through first-principles calculations. We found that the BN/SSnSe heterojunction is a type-II structure, with electron mobility (<em>μ</em><small>_e</small>) and hole mobility (<em>μ</em><small>_h</small>) of 1257.32 and 439.73 cm<small>²</small> V<small>⁻¹</small> s<small>⁻¹</small>, respectively. By modulating the interlayer spacing to 2.7 Å, we successfully achieved the desired photocatalytic band-edge positions (CBM &gt; −4.44 eV, VBM &lt; −5.67 eV). Additionally, we discovered a unique phenomenon in the oxygen evolution reaction (OER), where the peroxide groups (OOH) automatically detach when H<small>⁺</small> is adsorbed on the reaction intermediate *OOH, leading to the production of O<small>₂</small> and H<small>₂</small>. We refer to this process as the H-ion induced desorption mechanism (H-IIDM). This mechanism not only enables the separation of the OER and hydrogen evolution reaction (HER) on different surfaces but also further enhances the photocatalytic efficiency. Furthermore, the BN/SnSSe heterojunction exhibits excellent visible-light absorption with a high optical absorption coefficient (10<small>⁵</small> cm<small>⁻¹</small>), and BN/SSnSe has a high solar hydrogen production efficiency (32.61%), significantly outperforming conventional 2D photocatalysts. These findings suggest that the BN/SnSSe heterojunction holds great potential as a photocatalyst for water splitting applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"183 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745321","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":"On the Nature of Ion Aggregation in EC-LiTFSI Electrolytes","authors":"Hema Teherpuria, Prabhat Jaiswal, Santosh Mogurampelly","doi":"10.1039/d4cp04606d","DOIUrl":"https://doi.org/10.1039/d4cp04606d","url":null,"abstract":"We investigate the structural and dynamic properties of concentrated ethylene carbonate (EC)-LiTFSI (lithium bis(trifluoromethanesulfonyl)imide) electrolytes using molecular dynamics (MD) simulations to elucidate the molecular mechanisms governing ion aggregation and transport. Increasing salt concentration induces a transition in the local solvation environment, marked by reduced radial distribution functions for ion-ion and ion-solvent interactions. This shift reflects the formation of ion pairs and larger ionic clusters, altering electrostatic interactions and weakening Li⁺-EC solvation. Ion cation, peaks at= 0 for dilute salt concentrations,","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"38 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745742","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":"Gurney and cylinder wall velocities of explosives: analytical estimates and thermochemical simulations","authors":"Didier Mathieu","doi":"10.1039/d5cp00761e","DOIUrl":"https://doi.org/10.1039/d5cp00761e","url":null,"abstract":"Gurney velocity (uG) and cylinder wall velocity (vs) of energetic materials are calculated using the semi-empirical Cγ method, an analytical model previously developed for CHNO high explosives and presently extended to additional elements and to explosives at low loading density. The re- sults are compared to recent procedures based on thermochemical simulations. Regarding uG , both approaches perform similarly well for organic high explosives, with an average relative error close to 2.6%. However, Cγ underestimates uG for tritonal, an explosive with 20−40wt% aluminium powder. Regarding vs, a newly introduced empirical equation is shown to perform better than the Gurney model, although not as well as a recent correlation involving the detonation energy de- rived from thermochemical simulations, which are still required to predict cylinder wall experiments with optimal accuracy. With regard to the application of present models to the design of new materials, Cγ is not recommended for metal-containing compounds. However, for the high-thoughput design of organic high explosives, it is an invaluable tool allowing fast and reproducible calculations of Gurney energies with state-of-the-art accuracy. A very simple, hackable Python script is provided for this purpose.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"38 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745323","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":"Low-lying excited states of linear all-trans polyenes: the σ–π electron correlation and the description of ionic states","authors":"Julio C. V. Chagas, Luan G. F. dos Santos, Reed Nieman, Adelia J. A. Aquino, Silmar A. do Monte, Felix Plasser, Péter G. Szalay, Hans Lischka, Francisco B. C. Machado","doi":"10.1039/d5cp00339c","DOIUrl":"https://doi.org/10.1039/d5cp00339c","url":null,"abstract":"In this work, the electronic spectra of all-<em>trans</em> polyenes, from hexatriene to dodecahexaene are investigated. Special attention is given to the challenging description of the ionic 1<small>¹</small>B<small>⁺</small><small>_u</small> state. A comprehensive wavefunction analysis of both singlet (2<small>¹</small>A<small>⁻</small><small>_g</small>, 1<small>¹</small>B<small>⁺</small><small>_u</small>, and 2<small>¹</small>B<small>⁻</small><small>_u</small>) and triplet excited states (1<small>³</small>A<small>⁻</small><small>_g</small> and 1<small>³</small>B<small>⁻</small><small>_u</small>) is performed using a range of multireference correlated methods, including multireference configuration interaction with singles and doubles (MR-CISD) including <em>a posteriori</em> size-extensivity Pople correction (+P), and the multireference averaged quadratic coupled-cluster (MR-AQCC) method. While covalent states are well described by multi-configurational self-consistent field (MCSCF) theory, accurately describing the ionic state requires addressing size-extensivity errors, basis set effects, and, most importantly, σ–π electron correlation. Taking these factors into account, MR-CISD+P and MR-AQCC results mutually corroborate that the ionic 1<small>¹</small>B<small>⁺</small><small>_u</small> state is the first vertically excited state in hexatriene and octatetraene. In decapentaene, extrapolated MR-CISD+P results indicate that the 2<small>¹</small>A<small>⁻</small><small>_g</small> and 1<small>¹</small>B<small>⁺</small><small>_u</small> states are nearly degenerate, while MR-AQCC suggests that the ionic state lies approximately 0.2 eV below the covalent state. From a wavefunction perspective, the ionic state is consistently well-represented by a single HOMO–LUMO excitation, whereas the contribution of doubly excited configurations increases with chain length for both covalent states.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"32 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745324","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":"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 (&gt; 100 mM), the majority of DDholes were captured via an ultrafast pre-solvated pathway in &lt; 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}