Physical Chemistry Chemical Physics最新文献

{"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":"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":"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}

{"title":"Beyond inert: how carbon supports tune the oxygen evolution activity of polyoxometalate-based single-atom catalysts.","authors":"Mengke Wang, Guang-Jie Xia","doi":"10.1039/d6cp02872a","DOIUrl":"https://doi.org/10.1039/d6cp02872a","url":null,"abstract":"<p><p>Phosphomolybdic acid (PMA)-based single-atom catalysts (SACs) are promising for the oxygen evolution reaction (OER), but the role of their ubiquitous carbon support has rarely been investigated. Using density functional theory (DFT), we systematically investigated the OER on TM₁/PMA (TM = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt; PMA = [PMo₁₂O₄₀]^3-) with no support, a pristine carbon support, a hydroxyl (-OH)-functionalized support, and a carboxyl (-COOH)-functionalized support. We found that the mere presence of carbon support strongly modulates catalytic activity, an effect that far outweighs that of its subsequent functionalization. Bader charge analysis reveals significant electron donation from the carbon support to the TM₁/PMA unit, markedly altering intermediate adsorption free energies, which in turn either improves or worsens OER performance by shifting the metals along the descriptor axis and slightly lowering the volcano apex. For example, the Ni₁/PMA@C achieves a low overpotential of 0.37 V, markedly lower than 0.70 V for bare Ni₁/PMA. This support-induced modulation carries a critical methodological implication: for single-metal-on-anion SAC systems such as PMA-based catalysts, the carbon support must be explicitly included in theoretical models to capture its essential charge transfer with SAC. The carbon support is far from an inert scaffold but is a key factor in designing high-efficiency PMA-based single-atom OER catalysts.</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":"149190119","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":"Janus Ga 2 XTe (X = S, Se) monolayers under hydrostatic pressures: Stability and tunable optoelectronic properties","authors":"Huabing Shu,Jiyuan Guo,Haiying Xu","doi":"10.1039/d6cp02746f","DOIUrl":"https://doi.org/10.1039/d6cp02746f","url":null,"abstract":"Using DFT+G 0 W 0 +BSE methods, the stability and optoelectronic characteristics of Ga 2 XTe (X = S, Se) monolayers are examined systematically, with particular focus on the effects of hydrostatic pressure. Phonon dispersion spectra validate the dynamical stabilities of the pristine monolayers. G 0 W 0 calculations reveal that these monolayers possess moderate direct bandgaps of ~ 2 eV. Their dynamical stability can be kept under pressures up to 2 (3) GPa for the Ga 2 STe (Ga 2 SeTe), and the bandgap can be significantly modulated under the observed pressures. Though the Bethe-Salpeter equation (BSE), the optical responses of the two Janus monolayers are explored and significant exciton peaks are identified. Interestingly, exerting pressure on the Janus Ga 2 SeTe monolayer significantly modifies the photo-induced transitions, leading to a pronounced red-shift and increased absorption for the visible and near-infrared lights.Additionally, the exciton binding energy in both monolayers decreases significantly with increased pressures, indicating easier exciton dissociation. Our findings suggest that these Janus monolayer materials hold potential as candidates for optoelectronic","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"11 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173162","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":"Chemical control of hydrogen cage geometry and electron–phonon coupling in cubic NaXH superconducting hydrides","authors":"Jing-Ting Zhou,Zhen Jiao,Zhi-Yuan Qiu,Wen-Guang Li,Miao Zhang,Zheng-Tang Liu,Qi-Jun Liu","doi":"10.1039/d6cp03196j","DOIUrl":"https://doi.org/10.1039/d6cp03196j","url":null,"abstract":"Hydrogen-rich hydrides are promising candidates for high-temperature superconductivity under megabar pressures. In this work, we perform systematic first-principles calculations on cubic Pm3̄m ternary hydrides NaXH12, which serve as a fixed hydrogen-framework platform to tune hydrogen cage geometry via central metal atom substitution. All compositions stabilize an intact H24 cage via combined ionic metal–hydrogen interactions and covalent intra-cage H–H bonds, and their dynamical stability exhibits a systematic variation with the atomic radius of X. Larger central X atoms expand the H24 framework and elongate average H–H bonds, which softens mid-frequency hydrogen vibrational modes and amplifies the overall electron–phonon coupling dominated by the hydrogen sublattice. By contrast, external pressure compresses the hydrogen cage, hardens hydrogen phonon branches and suppresses coupling strength. At 200 GPa, the superconducting transition temperatures of the relevant compounds, calculated via the Allen–Dynes modified McMillan equation, range from 199.14 to 225.30 K, with NaYH12 reaching a maximum Tc of 225.30 K. This work establishes an effective chemical tuning route for hydrogen clathrate superconductors: atom radius engineering modulates H–H bonding, hydrogen phonon softening and superconducting performance, providing guidance for optimizing superconducting performance through chemical tuning of the hydrogen cage geometry.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"53 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173164","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":"Organic small molecule modifies the perovskite layer to prepare efficient and stable inverted perovskite solar cells.","authors":"Mengyan Feng, Binbin Wang, Shilong He, Supeng Gao, Yaowu Wang, Yue Han, Tao Li, Shuguang Cao, Lavrenty G Gutsev, Yao Li","doi":"10.1039/d6cp02893d","DOIUrl":"https://doi.org/10.1039/d6cp02893d","url":null,"abstract":"<p><p>The perovskite layer is the core component of perovskite solar cells (PSCs), and the quality of the perovskite film critically impacts the performance of PSCs. Interfacial contact optimization, defect passivation, and energy level alignment regulation are effective approaches to fabricate high-performance PSCs. Herein, an organic small molecule, 5-bromopyridine-2,3-dicarboxylic acid (BPDCA), is doped into a perovskite precursor solution to serve as the photosensitive layer of PSCs. Density functional theory (DFT) simulations and systematic characterizations confirm that BPDCA can optimize the crystallization quality of the perovskite and passivate defects in the perovskite film through the N atom on the pyridine ring and the O atom on the carboxyl group. Meanwhile, BPDCA doping optimizes the energy level matching, promotes the extraction and transport of charges, and enhances the open-circuit voltage (<i>V</i>_oc). The PSCs fabricated with BPDCA doping achieve a power conversion efficiency (PCE) of 20.75%, with a <i>V</i>_oc of 1.13 V. The unencapsulated device maintains more than 90% of the initial PCE after 1000 h of exposed storage in an air atmosphere. This work offers a straightforward and effective strategy for obtaining efficient and stable PSCs through functionalized perovskites.</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":"149178034","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}