Physical Chemistry Chemical Physics最新文献

{"title":"Computational Insights into Defect Induced Modulation in Electronic Properties of 2D Nitride Monolayers","authors":"Shreya Sarkar,Kuneh Parag,Brahmananda Chakraborty","doi":"10.1039/d6cp00158k","DOIUrl":"https://doi.org/10.1039/d6cp00158k","url":null,"abstract":"Two-dimensional (2D) nitride materials such as hexagonal boron nitride (h-BN), graphitic carbon nitride (g-C₃N₄), and Beryllonitrene (BeN₄) have emerged as promising candidates for next-generation electronic, optoelectronic, and energy applications due to their unique structural and electronic properties. This study presents a systematic investigation of the effects of vacancy defect, specifically the role of nitrogen and constituent atom vacancies on the electronic properties of these materials. Our findings reveal that the introduction of nitrogen vacancies significantly alters the electronic characteristics of these materials. In h-BN, the presence of a nitrogen monovacancy significantly lowers the work function from 5.97 eV to 3.45 eV.Additionally, this defect reduces the band gap from 4.6 eV to 0.64 eV, driving the material toward half-metallic behaviour. This is accompanied by the emergence of flat bands near the Fermi level, indicative of strong electron-electron interactions. In g-C₃N₄, nitrogen vacancies lead to a decrease in work function and band gap, with double nitrogen vacancies rendering the material nearly metallic. In BeN₄, nitrogen vacancies result in minimal charge redistribution and a slight increase in work function, highlighting the material's unique electronic behaviour. These results underscore the potential of vacancy engineering in tuning the electronic properties of 2D nitride materials, offering avenues for the design of materials with tailored work functions and band gaps for applications in optoelectronics, spintronics, and catalysis.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"42 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218286","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":"Spacer-controlled morphology and mixed ionic-electronic transport in 2D Ruddlesden-Popper perovskites.","authors":"Fábio S A Abud, Adelino C Handa, José Romão Franca, Jose Antonio Souza","doi":"10.1039/d6cp03040h","DOIUrl":"https://doi.org/10.1039/d6cp03040h","url":null,"abstract":"<p><p>Two-dimensional Ruddlesden-Popper (RP) halide perovskites are promising alternatives to 3D analogues because their layered structures can improve environmental stability and partially suppress ion migration. At the same time, the insertion of bulky organic spacers enhances structural anisotropy and excitonic confinement, making charge transport strongly dependent on film morphology and crystallographic orientation. Here, we investigate the layered iodide perovskites PEA₂PbI₄ and MeOPEA₂PbI₄, employing phenethylammonium (PEA) and 4-methoxyphenethylammonium (MeOPEA) as closely related organic spacers. The methoxy substitution provides a small perturbation of intermolecular interactions and crystallization kinetics while preserving the <i>n</i> = 1 RP framework. X-ray diffraction confirms phase-pure layered structures for both compounds, while optical measurements reveal pronounced excitonic confinement with optical gaps of 2.27 and 2.33 eV for PEA₂PbI₄ and MeOPEA₂PbI₄, respectively. Despite these similarities, hot-cast films exhibit markedly different microstructures, with MeOPEA₂PbI₄ having a compacted microcrystalline arrangement, whereas PEA₂PbI₄ displays a porous, heterogeneous morphology. Electrical measurements reveal pronounced hysteresis, and slow polarization dynamics characteristic of mixed ionic-electronic conduction. Under illumination, photoconductivity emerges predominantly in the out-of-plane geometry, highlighting the role of grain-boundary connectivity and orientation-dependent transport pathways. Transient measurements further show that light-induced ionic redistribution remains active in these layered films. Overall, the results demonstrate that subtle spacer modification controls optoelectronic behavior primarily through its influence on crystallization and mesoscale connectivity.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149190129","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 and stabilization of surface nitrogen nanobubbles on mica.","authors":"Xinyuan Nie, Zhanli Geng, Yujie Huang, Chonghai Qi, Yongquan Zhou, Lijuan Zhang, Xingya Wang, Yanwei Wang, Chunlei Wang","doi":"10.1039/d6cp02327d","DOIUrl":"https://doi.org/10.1039/d6cp02327d","url":null,"abstract":"<p><p>Nanobubbles are of critical importance in mineral flotation and surface cleaning, due to their high stability and large specific surface area. Surface nanobubbles have been most commonly observed on hydrophobic or weakly wetting substrates, such as graphite; however, substrate hydrophobicity is not a strict prerequisite for their stability. In this study, stable nanobubbles were experimentally observed on superhydrophilic muscovite, motivating an investigation of their interfacial stabilization mechanism. To elucidate this behavior, we investigate the adsorption and stabilization mechanisms of nanobubbles on the muscovite (001) surface using molecular dynamics simulations. The simulations demonstrate that nanobubbles can stably adsorb onto the mica surface, reaching an internal density of 443 kg m^-3. An interfacial water layer exists between the nitrogen gas and the interface, characterized by ordered hydrogen bond orientations and distinct hydrophobic properties, which collectively inhibit bubble diffusion and promote stability. Furthermore, the stable existence of nanobubbles on the mica surface was observed using quantitative nanomechanical atomic force microscopy (AFM). The stability of the nanobubbles is closely related to the structure of interfacial water, where high-density bubble structures, weak interlayer hydrogen bonding, and ordered hydrogen bond networks serve as the key factors for stable adsorption. These findings provide a theoretical foundation for understanding the microscopic mechanisms of nanobubbles at the solid-liquid interface.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149190265","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":"Atomistic-scale study on the role of CNT as a nucleating agent of α-Al in Al-CNT composite.","authors":"Indrani Mukherjee, Jai Vignesh, Aditya Anand, Prosenjit Das","doi":"10.1039/d6cp03568j","DOIUrl":"https://doi.org/10.1039/d6cp03568j","url":null,"abstract":"<p><p><i>Ex situ</i> reinforcement of the A356 alloy with multi-walled carbon nanotubes (MWCNTs) markedly refines the solidification microstructure by increasing the nucleation density of the primary aluminium phase. Atomic-scale simulations are performed in the present work to capture the mechanism behind the increased nucleation of α-Al grains during the solidification of the A356 alloy due to the presence of a CNT within the melt, employing density functional theory and molecular dynamics simulations. First-principles DFT calculations are performed within the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) functional with projector augmented wave (PAW) pseudopotentials to reliably capture the highly localized chemical bonding, charge transfer, and electronic hybridization at the metallic Al-CNT contact plane. Interfacial energy parameters, electronic density of states (DOS), and phonon density of states (PDOS) are extracted using density functional theory for the Al-CNT composite structure. Furthermore, the changes in the diffusion coefficient of Al atoms in the liquid state due to the presence of the CNT are calculated using the molecular dynamics simulation technique. The simulation results demonstrate strong chemical bonding at the Al-CNT interface, the presence of the CNT as a stiff substance within the Al matrix in the melt state and a reduction in the diffusion coefficient of Al atoms due to CNT inclusion, which are in excellent agreement with the experimental observations of the increased heterogeneous nucleation of α-Al grains during the solidification of the Al-CNT composite.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149190204","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":"Niobium-substituted group III nitride nanocages: A series of inorganic single superatom catalysts for Suzuki reaction","authors":"Wei-Huang Wang,Zhi-Chao Zhang,Xin-Yu Shi,Yao Chen,Min-Ning Du,Wei-Ming Sun","doi":"10.1039/d6cp03120j","DOIUrl":"https://doi.org/10.1039/d6cp03120j","url":null,"abstract":"Suzuki coupling reaction, a widely used reaction for C-C bond formation in pharmaceutical synthesis, still largely depends on the homogeneous Pd catalysts that suffer from high cost, difficult recovery, and metal residue issues. In this work, a new type of single superatom catalysts (SSCs) were designed by substituting a Nb atom for one M atom of M12N12 (M = B, Al, and Ga) to form a palladium-like NbN superatom unit within these SSCs, namely NbN@M11N11 (M = B, Al, and Ga). Our results demonstrate that these catalysts exhibit remarkable catalytic activity for Suzuki reaction, and therein, NbN@B11N11 exhibits superior catalytic performance to the conventional Pd(PPh3)2 catalyst. Furthermore, an inverse size-activity relationship has been observed for NbN@Bn-1Nn-1 (n = 12, 16, 24), where smaller nanocage size results in superior catalytic performance. This study confirms that constructing a Pd-like superatom subunit in group III nitride nanocages can realize new catalysts for Suzuki reaction and thus provides novel pathways for designing and synthesizing SSCs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"50 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173160","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":"The vibronic landscape of excitons in photosynthetic antennae.","authors":"Manuel J Llansola-Portoles, James Sturgis, Andrew Gall, Juan J Romero, Andrew A Pascal, Leonas Valkunas, Bruno Robert","doi":"10.1039/d6cp02540d","DOIUrl":"https://doi.org/10.1039/d6cp02540d","url":null,"abstract":"<p><p>Light harvesting and excitation energy transfer in photosynthesis generally involve chlorophyll molecules held by their host proteins at short distances from each other, resulting in excitonic coupling. The transfer of excitation energy to the reaction centres consists of exciton migration and relaxation within and between photosynthetic proteins. The dynamics of this process depend on excitonic coupling between the pigments, on the energy gaps and reorganisation energies of the excited states involved, on the disorder imposed by the proteins, and on the vibrational modes resonant with these gaps. The precise structures and vibrational landscapes of excitons are thus essential knowledge for understanding the amazing efficiency of photosynthesis. In this work, we characterise the vibrational properties of excitons in light-harvesting proteins from purple photosynthetic bacteria, which indicate on how many bacteriochlorophylls they reside and suggest in which proportions. Vibrational spectra obtained from bacteriochlorophylls in proteins generally contain additional vibronic contributions when compared to isolated pigments, which could open additional pathways for vibrationally assisted excitation energy transfer. In contrast, the absence of new vibronic contributions in the spectra of the chlorophyll-containing proteins studied here above 100 cm^-1 suggests that in these complexes, vibrationally assisted excitation energy transfer occurs through the vibrational modes of chlorophyll molecules in an equilibrium configuration.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149190109","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":"Structural disorder driven component dependent decomposition pathways and intermolecular interactions in HMX/1,4-PDCA energetic cocrystals: an ab initio molecular dynamics study","authors":"Umair Afzal,Mengyun Mei,Weihua Zhu","doi":"10.1039/d6cp02273a","DOIUrl":"https://doi.org/10.1039/d6cp02273a","url":null,"abstract":"Structural disorder in energetic cocrystals is recognized to influence their decomposition behavior, yet the underlying trends remain largely unexplored. In this work, the early-stage decomposition pathways and intermolecular interactions of both crystalline and amorphous HMX/1,4-PDCA cocrystals are investigated via ab initio molecular dynamics simulations at 2500 K. Hirshfeld surface analysis reveals that the intermolecular environment in the amorphous model experiences greater strain, characterized by fewer O···H contacts alongside increased O···O and N···O interactions, which ultimately shape the decomposition behavior. In both models, the decomposition of the cocrystal is initiated by the breakdown of HMX; however, the dominant initiation pathway critically depends on molecular packing. Specifically, the crystalline model decomposes via H-dissociation, whereas the amorphous model preferentially undergoes nitro group dissociation. Structural disorder exerts a component-dependent effect, favoring HMX decomposition while simultaneously inducing more complex and heterogeneous degradation behavior in 1,4-PDCA. The amorphous system exhibits higher initial potential energy, faster fragmentation, and enhanced atomic mobility, all pointing to accelerated decomposition kinetics. In contrast, the crystalline model displays lower final potential energy and greater yields of stable products such as H₂O and N₂, suggesting a more thermodynamically complete reaction pathway. Collectively, these findings provide valuable insights into the role of structural disorder in modulating intermolecular interactions and decomposition mechanisms in energetic cocrystals.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"85 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173159","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":"Application of one-step synthesized broadband carbon quantum dots in white light-emitting diodes.","authors":"Jia Liu, Hailong Yu","doi":"10.1039/d6cp02828d","DOIUrl":"https://doi.org/10.1039/d6cp02828d","url":null,"abstract":"<p><p>In recent years, white light-emitting diodes (W-LEDs) based on carbon quantum dots (CQDs) have received widespread attention, with most researchers fabricating W-LEDs using multi-color CQDs. In this study, white CQDs (W-CQDs) were synthesized <i>via</i> a one-step solvothermal method using <i>o</i>-phenylenediamine and 1,2,4-benzenetricarboxylic acid as the carbon precursors and absolute ethanol as the solvent. The morphology, size, surface functional groups, composition, and crystal structure of W-CQDs were characterized using transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction techniques. The wide bandgap and broad-spectrum luminescence properties of W-CQDs demonstrate their potential application in W-LEDs. We employed a double-layer encapsulation method using polyvinyl alcohol and epoxy resin adhesives A and B to fabricate W-LED devices based on W-CQDs. These devices exhibit color coordinates of (0.32, 0.38), a color rendering index of 88, and a correlated color temperature of 5656 K. This study provides a simple method to synthesise CQDs for application in W-LED devices while extending their operational lifespan.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177878","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":"Dual-Guest-Metal Control of Stability and Superconductivity in Ambient-Pressure B-C Clathrates X 0.5 Y 0.5 B 2 C 8","authors":"Yuting Yang,Zhangmin Su,Ruijie Chen,Hongying Guo,Xinyue Liu,Yimei Fang,Feng Zheng","doi":"10.1039/d6cp03160a","DOIUrl":"https://doi.org/10.1039/d6cp03160a","url":null,"abstract":"Phonon-mediated superconductivity in boron-carbon clathrates has become an active area of research, but how mixed guest-metal occupancy affects stability and superconductivity is still unclear. Using high-throughput first-principles calculations, we study quaternary X0.5Y0.5B2C8 clathrates (X, Y = Li, Na, K, Rb, Cs, Mg, Ca, Sr, and Ba) at ambient pressure. We identify 15 dynamically stable phases, all involving combinations of two large-radius guest metals. Fourteen of these phases are predicted to be superconducting: compounds with an average guest oxidation state of +1.5 and +1 show Tc of 34 to 40 K and 85 to 94 K, respectively, whereas the remaining +2 phase is semiconducting. The contrast in Tc fits a rigid-band picture in which lower guest oxidation states increase the B-C density of states at the Fermi level and enhance coupling to mid-frequency B-C phonons. Ab initio molecular dynamics at 300 K reveals no structural transformation, indicating that these dual-guest clathrates are viable candidates for further study.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"53 4 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173154","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":"Coordinated transcriptional and translational resource allocation shapes gene expression","authors":"Mahima Mahima,Ajeet Kumar Sharma","doi":"10.1039/d6cp02090a","DOIUrl":"https://doi.org/10.1039/d6cp02090a","url":null,"abstract":"The coordinated interplay of transcription and translation govern the overall rate of protein synthesis. Although this coordination of transcription and translation has been widely studied in different contexts, how it shapes cellular resource utilization and global transcriptional–translational resource allocation remains unclear. To address this, we reformulate the conventional Totally Asymmetric Simple Exclusion Process (TASEP) α − β phase diagram into a biologically relevant α − ω representation, where initiation (α) and elongation (ω) rates reflect investment in molecular machinery and substrate-dependent translocation, while β represents the termination rate. In this α − ω representation, the conventional low-density (LD), high-density (HD), and maximal-current (MC) classifications no longer characterize these TASEP regimes and are instead more naturally interpreted as initiation-limited (IL), termination-limited (TL), and elongation-limited (EL) regimes, respectively. Then, mapping E. coli genes onto this phase space reveals that they predominantly occupy the initiation-limited (IL) regime, where ribosome utilization efficiency is optimized despite lower protein synthesis flux, suggesting cells prioritize efficient resource utilization over maximal protein production capacity. We further show that transcriptional and translational resource-utilization efficiencies are intrinsically coupled, such that improving resource utilization in one process may increase the biosynthetic burden on the other. Consequently, local optimization of transcriptional or translational throughput alone does not necessarily maximize the global efficiency of protein production, which instead emerges from coordinated tuning of both processes. Then, using constrained optimization with Lagrangian multipliers, we identify optimal transcriptional and translational resource-allocation strategies that minimize biosynthetic cost and define an upper bound on achievable resource-utilization efficiency. This analysis reveals how coordinated tuning of transcriptional and translational initiation rates can enable efficient cellular resource allocation. Together, these findings suggest efficient gene expression is governed by global resource-allocation constraints arising from molecular traffic during transcription and translation.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"3 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173152","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}