Physical Chemistry Chemical Physics最新文献

{"title":"Dual-Surface Functionalization of Graphene beyond DFT Limits: Nanoscale Insights into Flat Bands and Optical Behavior","authors":"Nasim Hassani, Ayoub Esmailpour, Mehdi Neek-Amal, François M. Peeters","doi":"10.1039/d5cp00040h","DOIUrl":"https://doi.org/10.1039/d5cp00040h","url":null,"abstract":"Graphene's exceptional electronic and optical properties make it a promising material for advanced technologies. We performed Density Functional Tight Binding (DFTB) simulations to explore the formation of flat electronic bands in graphene unctionalized with epoxy and hydrogen groups. By varying the density of functional groups, we identified the emergence of isolated flat bands at critical functional densities, especially beyond 10 hydrogen and 10 oxygen atoms per 72 carbon atoms. Larger supercells (288C-48H-48O) showed the formation of 14 parallel flat bands, emphasizing the impact of high functional group density. Additionally, odd numbers of H and O atoms induced midgap states. Increasing the functionalization ratio (30%) preserved the integrity of the surface modifiers, enhancing binding energy, unit cell constants, and structural stability. Optical properties, including dielectric function, conductivity, and absorption, exhibited distinct shifts with varying functional densities. These results highlight the tunability of graphene's electronic and optical behavior, providing insights for customized graphene-based materials in future electronic and photonic applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"238 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766424","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":"Carrier-generation mechanism in Zn-doped In2O3 transparent conductors","authors":"Sanghyuk Lee, Seungwon Shim, Hyunwoo Jang, Jae Kyeong Jeong, Youngho Kang","doi":"10.1039/d5cp00408j","DOIUrl":"https://doi.org/10.1039/d5cp00408j","url":null,"abstract":"Zn-doped In<small>₂</small>O<small>₃</small> (IZO) has been extensively studied as a transparent conducting oxide (TCO) due to its favorable optical and electrical characteristics. In this work, to uncover the origin of degenerate <em>n</em>-type doping in IZO, we investigated point defects using density functional theory (DFT) calculations. Among the two possible configurations of Zn dopants, namely interstitial (Zn<small>_<em>i</em></small>) and substitutional Zn (Zn<small>_In</small>), Zn<small>_In</small> is found to be energetically more favorable. While Zn<small>_In</small> acts as an acceptor, potentially compensating for <em>n</em>-type doping, it readily forms a defect complex, Zn<small>_In</small>–<em>V</em><small>_O</small>, by combining with oxygen vacancies (<em>V</em><small>_O</small>s), the dominant intrinsic defects in In<small>₂</small>O<small>₃</small>. This defect complex exhibits a substantial binding energy of approximately 1 eV and functions as a shallow donor. By evaluating carrier concentrations that can occur in IZO films, we demonstrate that the formation of Zn<small>_In</small>–<em>V</em><small>_O</small> is critical to maintaining or even enhancing significant <em>n</em>-type conductivities of IZO. By elucidating the doping behavior of IZO, this work provides critical insights to optimize its properties, thereby helping the advancement of optoelectronic and energy devices where IZO serves as a vital TCO.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"107 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766422","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":"Unusual Mechanism of Aziridine Biosynthesis Catalysed by an αKGdependent Non-heme Enzyme TqaL","authors":"Warispreet Singh, M. Huang","doi":"10.1039/d4cp03708a","DOIUrl":"https://doi.org/10.1039/d4cp03708a","url":null,"abstract":"Aziridines are present in many synthetic pharmaceuticals. The synthesis of aziridine ring remains challenging due to its highly strained three-membered ring structure. Recently, a non-heme αKG-dependent enzyme TqaL have been demonstrated to catalyze the synthesis of aziridines from L-Val. However, the detailed reaction mechanism of the enzyme remains elusive. Here, we report, the mechanism of oxidative cyclisation for aziridine synthesis catalyzed by TqaL. Following the hydrogen atom abstraction step, the reaction proceeds via a unique concerted process with single electron transfer from the isopropyl radical to the Fe(III)-OH motif, which is coupled with the electrophilic attack of the primary amine substrate to the tertiary isopropyl radical and simultaneous proton transfer from the substrate amine to the hydroxyl group of the Fe(III)-OH to give aziridine. This research would provide valuable structural basis for tailoring the non-heme αKG-dependent enzyme for the biosynthesis of highly active aziridinederivatives as pharmaceuticals.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"176 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758502","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: Gas-phase, conformer-specific infrared spectra of 3-chlorophenol and 3-fluorophenol","authors":"Olga A. Duda, Alexander K. Lemmens, Gerrit C. Groenenboom, Daniel A. Horke, Joost M. Bakker","doi":"10.1039/d5cp90068a","DOIUrl":"https://doi.org/10.1039/d5cp90068a","url":null,"abstract":"Correction for ‘Gas-phase, conformer-specific infrared spectra of 3-chlorophenol and 3-fluorophenol’ by Olga A. Duda <em>et al.</em>, <em>Phys. Chem. Chem. Phys.</em>, 2025, https://doi.org/10.1039/d4cp04352a.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"183 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758505","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":"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":"Unlocking the Sensing and Scavenging Potential of Sc2CO2 and Sc2CO2/ TMD Heterostructures for Phosgene Detection","authors":"Julaiba Tahsina Mazumder, Mohammed Mehedi Hasan, Fahim Parvez, Tushar Shivam, Dobbidi Pamu, Alamgir Kabir, Mainul Hossain, Ravindra Kumar Jha","doi":"10.1039/d5cp00601e","DOIUrl":"https://doi.org/10.1039/d5cp00601e","url":null,"abstract":"The detection of phosgene is critically important due to its extreme toxicity and potential use as a chemical warfare agent to ensure public safety and security. Two-dimensional (2D) scandium carbide MXenes (Sc2CTx; T=O–, x=2) stands out as a promising material for gas sensing applications due to their unique electronic and adsorption properties. In this study, the first-principle calculations based on the GGA-PBE functional was employed to investigate the structural, electronic, and mechanical characteristics of Sc2CO2 with different positions of surface termination. The adsorption behavior of Sc2CO2 was systematically explored towards various gas molecules including N2, O2, CO, NO, CH4, H2S, and notably, phosgene (COCl2). Specifically, phosgene exhibits a high adsorption energy, highlighting the material’s selectivity towards this toxic gas. Furthermore, this study investigates the impact of gas adsorption on the electronic structure of Sc2CO2. The strategies such as, increasing operating temperatures and forming heterostructures with transition metal di-chalcogenides (MoSe2, WSe2), have proven to be highly effective to mitigate the challenges related to slow recovery time. This work underscores the potential of Sc2CO2 MXenes as highly sensitive and selective gas sensors, particularly for phosgene sensing.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"42 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758523","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}