The Journal of Physical Chemistry Letters最新文献

Multi-Barrel Nanopipets as a Model System for Quantifying Interpore Interactions and Superadditive Transport

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-11-11 DOI: 10.1021/acs.jpclett.6c02789

Anthony Dougman Cho,Claudia Evodie Puspa Dewi,Ethan Cao,Kelly L. Vernon,Cody W. Leasor,Tilman E. Schäffer,Lane A. Baker,Zuzanna S. Siwy

{"title":"Multi-Barrel Nanopipets as a Model System for Quantifying Interpore Interactions and Superadditive Transport","authors":"Anthony Dougman Cho,Claudia Evodie Puspa Dewi,Ethan Cao,Kelly L. Vernon,Cody W. Leasor,Tilman E. Schäffer,Lane A. Baker,Zuzanna S. Siwy","doi":"10.1021/acs.jpclett.6c02789","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02789","url":null,"abstract":"Developing advanced neuromorphic ionic devices requires a quantitative understanding of how neighboring nanopores interact within arrays. Crosstalk between adjacent pores is especially important because overlapping depletion zones can suppress current and cause the current through a parallel-pore array to be lower than the sum of currents through isolated pores. Here, using dual-barrel nanopipets as a model two-pore array, we show that interacting barrels connected in parallel can also produce superadditive transport, where the combined current exceeds the sum of currents through two independently measured barrels. Conductance enhancement is observed when closely spaced barrels carry opposite surface charges, with one barrel negatively charged and the other positively charged. Poisson–Nernst–Planck and Navier–Stokes continuum modeling further clarifies the role of ion concentration polarization. The models indicate that applying voltage across neighboring, oppositely charged pores creates an ion-enriched zone at the entrance of one barrel that feeds the depletion zone at the entrance of the second barrel, thereby mitigating ion concentration polarization and increasing the combined conductance. These experiments and models advance understanding of electrically and chemically addressable, interacting nanopores for future ionic circuits.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"23 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Unveiling the Phase Transformation Mechanism in BN from Large-Scale Machine Learning Molecular Dynamics

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-11-10 DOI: 10.1021/acs.jpclett.6c02892

Jaeyoung Cho,Nikhil Rampal,Stephen E. Weitzner,Graeme Henkelman,Liwen F. Wan

{"title":"Unveiling the Phase Transformation Mechanism in BN from Large-Scale Machine Learning Molecular Dynamics","authors":"Jaeyoung Cho,Nikhil Rampal,Stephen E. Weitzner,Graeme Henkelman,Liwen F. Wan","doi":"10.1021/acs.jpclett.6c02892","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02892","url":null,"abstract":"Boron nitride (BN) exhibits rich polymorphism, including cubic, hexagonal, rhombohedral, and wurtzite phases, whose dynamic transformations govern the stability and performance of BN-based materials in modern electronics, quantum photonics, and energy devices. Despite their technological importance, the atomistic mechanisms underlying its phase evolution remain poorly understood. Here, we use large-scale molecular dynamics simulations with a MACE-based machine learning interatomic potential. The potential is trained on high-fidelity density functional theory data and validated against ab initio molecular dynamics simulations to investigate phase transformation pathways in crystalline BN. We identify a layer-by-layer transformation mechanism that is initiated at heterogeneous BN interfaces, where local structural reconstruction propagates into neighboring crystalline regions. We further show that the transformation propensity depends on the interfacial structure and crystallographic orientation. These results provide atomistic insight into BN phase transformations under diverse thermodynamic conditions, while the associated MACE training workflow offers a generalizable framework for studying phase transformation mechanisms in other complex materials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"18 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374868","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Charge Transfer from Ammonia Neutralizes Propylene Oxide Cations: Implications for the Astrochemistry of Chiral Molecules

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-11-10 DOI: 10.1021/acs.jpclett.6c02696

Sanjana Maheshwari,Darya Kisuryna,Leah G. Dodson

引用次数: 0

Photoregulated Oxidase-Mimicking and Antibacterial Activity with Cascade Catalysis Probed by Copper Nanoclusters

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-11-10 DOI: 10.1021/acs.jpclett.6c03102

Khokan Paria,Paritosh Mahato,Preeti Sagarika,Chandan Sahi,Saptarshi Mukherjee

{"title":"Photoregulated Oxidase-Mimicking and Antibacterial Activity with Cascade Catalysis Probed by Copper Nanoclusters","authors":"Khokan Paria,Paritosh Mahato,Preeti Sagarika,Chandan Sahi,Saptarshi Mukherjee","doi":"10.1021/acs.jpclett.6c03102","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c03102","url":null,"abstract":"The development of light-responsive metal nanoclusters (MNCs) for showcasing photoregulated biomimicking catalysis and developing light-mediated potent antibacterial agents remains a central attraction of the present research. However, strategic modulation of the electronic structure in MNCs to impart light-triggered biocatalysis and antibacterial activity is associated with formidable challenges. In this study, the multidimensionally served enzymatic features in tyramine-protected CuNCs (Cu@Tyra NCs) have been comprehensively investigated, which display efficient peroxidase-like activity and a biocatalytic cascade upon coupling with a suitable natural enzyme. Upon visible light activation, photoexcited charge carriers in the Cu@Tyra NCs promote the generation of a hydroxyl radical (•OH) as a reactive oxygen species (ROS), which significantly enhances the catalytic efficiency. The photoinduced ROS also imparts strong antibacterial effects against Gram-negative bacteria (Escherichia coli) by inducing oxidative damage to cell membranes and intracellular components, exclusively in the presence of light.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374897","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Sampling Free Energy Landscapes of Ionic Colloidal Crystal Systems Using Machine-Learned Proxy Collective Variables

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-11-10 DOI: 10.1021/acs.jpclett.6c02885

Michael S. Chen,Stefano Sacanna,Glen M. Hocky

{"title":"Sampling Free Energy Landscapes of Ionic Colloidal Crystal Systems Using Machine-Learned Proxy Collective Variables","authors":"Michael S. Chen,Stefano Sacanna,Glen M. Hocky","doi":"10.1021/acs.jpclett.6c02885","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02885","url":null,"abstract":"Charged colloids coated with a polymer brush can be designed to preferentially self-assemble into different crystal structures by varying easy-to-tune experimental conditions. For a given set of conditions, we have observed in experiments and simulations a distribution of thermodynamically (meta)stable self-assembled crystal structures. Properly quantifying the free energy landscape of these colloidal systems is essential for rationally choosing conditions to preferentially target particular crystal structures. For some of the structures we have formed, standard crystalline order parameters are not able to differentiate between crystals or between crystals and amorphous aggregates. We show that local environment similarity descriptors are able to distinguish the relevant metastable states but are too expensive for use in biased MD simulations. Here, we adopt an approach from machine-learned interaction potentials showing that SE(3)-equivariant transformer networks can serve as an efficient-to-evaluate machine-learned proxy. As a result, we can compute the relative free energies of accessible colloidal structures as a function of different experimentally relevant physical knobs that can steer our system between two observed crystal types. As an example application, we then show how changing surface potentials of positive and negative colloids while maintaining the same attractive energy can shift which crystal structure is favored.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"8 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Transient Carrier Transport and Extraction in Passivated Perovskite Films

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-11-10 DOI: 10.1021/acs.jpclett.6c03195

Xiangyu Meng,Yuchao Liang,Xiayuan Xu,Yuxin Zhang,Qingsong Li,Bohan Li,Wei Liu,Lixin Xiao,Shufeng Wang

引用次数: 0

Mode-Resolved Phonon Damping and Anharmonicity in Mo2C: Insights from Temperature-Dependent Raman Spectroscopy

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-11-10 DOI: 10.1021/acs.jpclett.6c02994

Ashish Jyoti Borah,Sajal Rai,Ravi Dutt,Anchal Srivastava

{"title":"Mode-Resolved Phonon Damping and Anharmonicity in Mo2C: Insights from Temperature-Dependent Raman Spectroscopy","authors":"Ashish Jyoti Borah,Sajal Rai,Ravi Dutt,Anchal Srivastava","doi":"10.1021/acs.jpclett.6c02994","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02994","url":null,"abstract":"The lattice dynamics of metallic molybdenum carbide (Mo2C) is investigated through mode-resolved temperature-dependent Raman spectroscopy over the range of 80–296 K. The Raman-active modes at ∼143 and ∼223 cm–1 and the high-frequency mode at ∼658 cm–1 exhibit systematic frequency softening and line width broadening with an increase in temperature. The line width evolution is adequately described by a three-phonon anharmonic decay model, with normalized residuals below 5%, indicating that anharmonic phonon–phonon interactions provide the dominant contribution to the temperature-dependent line width within the investigated range. The temperature-independent residual line width is analyzed using an Allen-type framework to obtain effective upper-bound estimates of electron–phonon coupling λeff, which may include contributions from defect scattering and other temperature-independent broadening mechanisms. The extracted values decrease from 0.081 and 0.026 for the low- and intermediate-frequency modes, respectively, to 0.0019 for the high-frequency mode. This hierarchy reflects the mode dependence of the residual line width-derived effective parameters and is qualitatively consistent with the predominantly Mo-derived electronic states near the Fermi level and reported density functional perturbation theory (DFPT) calculations. The results establish anharmonic phonon interactions as the dominant temperature-dependent contribution to the line width, while the intrinsic electron–phonon contribution cannot be uniquely separated from other sources of residual broadening.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"20 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374867","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Breaking Water at Graphene Defects

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-11-10 DOI: 10.1021/acs.jpclett.6c02970

Samuel G. H. Brookes,IniOluwa C. Popoola,Fabian Berger,Kara D. Fong,Angelos Michaelides,Christoph Schran

{"title":"Breaking Water at Graphene Defects","authors":"Samuel G. H. Brookes,IniOluwa C. Popoola,Fabian Berger,Kara D. Fong,Angelos Michaelides,Christoph Schran","doi":"10.1021/acs.jpclett.6c02970","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02970","url":null,"abstract":"Water dissociation at solid surfaces underpins processes ranging from corrosion and catalysis to electrochemistry and photovoltaics. Defects often serve as reactive sites for dissociation, yet how solvation influences water dissociation at such sites remains poorly understood. Here, we use state-of-the-art machine-learned interatomic potentials to explore water dissociation at defective graphene–water interfaces. We show that solvation qualitatively changes the reaction mechanism at a graphene single vacancy (SV), opening pathways that are absent for an isolated water molecule. Whereas the gas-phase process proceeds via a single concerted channel, the solvated SV splits water through two competing pathways: a basic route forming SV–H and OH(aq)− ⁠, and an acidic route forming SV–OH and H3O(aq)+ ⁠. These lower-barrier pathways produce distinct chemisorbed intermediates that enhance graphene–water adsorption. Accordingly, even a simple carbon vacancy gives rise to unexpectedly rich interfacial chemistry, coupling surface chemistry to interfacial charge and wettability, with implications for carbon functionalization and nanofluidic transport.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"53 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374866","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Single- and Multiexciton Dynamics in Porphyrin Nanorings 卟啉纳米结构中的单激子和多激子动力学

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-11-09 DOI: 10.1021/acs.jpclett.6c02850

Erico M. Braun,Michael Jirasek,Harry L. Anderson,Stephen R. Meech,Ismael A. Heisler,Giovanni Bressan

{"title":"Single- and Multiexciton Dynamics in Porphyrin Nanorings","authors":"Erico M. Braun,Michael Jirasek,Harry L. Anderson,Stephen R. Meech,Ismael A. Heisler,Giovanni Bressan","doi":"10.1021/acs.jpclett.6c02850","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02850","url":null,"abstract":"Exciton transport in molecular assemblies is typically studied in linear chains and polydisperse aggregates, where chain ends perturb the electronic structure and structural inhomogeneity can obscure size-dependent trends. Molecular nanorings overcome both limitations. They are end-group-free macrocycles with well-defined sizes, while their dimensions can be synthetically tuned from a few to several tens of porphyrin units. Here, we use intensity-cycled femtosecond transient absorption spectroscopy to disentangle single-exciton and multiexciton dynamics in a series of fully conjugated molecular nanorings containing 6–40 Zn-porphyrin units. By isolating the third-, fifth-, and seventh-order nonlinear responses, we independently track single-, two-, and three-exciton dynamics, respectively, enabling the ring-size dependence of exciton–exciton annihilation (EEA) to be determined without relying on a priori kinetic assumptions. The EEA rate decreases systematically with an increase in ring size, accompanied by a crossover from annihilation-limited to diffusion-limited EEA between 20 and 30 porphyrin units. The smallest nanoring exhibits no resolvable multiexciton dynamics, consistent with exciton delocalization across the entire ring or equivalent subinstrument response EEA, whereas larger rings exhibit increasingly diffusive exciton motion as static disorder limits delocalization. The retrieved exciton diffusion coefficients are 2–3 orders of magnitude higher than those we previously reported, indicating that the assumptions inherent to conventional intensity-dependent fitting can substantially underestimate exciton mobility.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"25 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368343","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Carbon-Isotope Labeling Rules Out Covalent Sulfur Addition to Graphene 碳同位素标记排除共价硫添加到石墨烯

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-11-09 DOI: 10.1021/acs.jpclett.6c03114

Simon Sprocq,Elie Haddad,Léonard Schué,Vincent Lemelin,Mohammed Amine-Mezour,Pierre L. Lévesque,Mickael Dollé,Alain Rochefort,Richard Martel

{"title":"Carbon-Isotope Labeling Rules Out Covalent Sulfur Addition to Graphene","authors":"Simon Sprocq,Elie Haddad,Léonard Schué,Vincent Lemelin,Mohammed Amine-Mezour,Pierre L. Lévesque,Mickael Dollé,Alain Rochefort,Richard Martel","doi":"10.1021/acs.jpclett.6c03114","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c03114","url":null,"abstract":"Covalent functionalization of graphene is commonly inferred from Raman spectroscopy, photoelectron spectroscopy, microscopy, and first-principles calculations. However, these methods may not distinguish bonding to the graphene lattice from the adsorption of carbon-containing reaction products. Here, we investigate this ambiguity using the gas-phase reaction of sulfur radicals with graphene as a case study. Sulfur treatment produces new Raman bands, substantial changes in the photoemission spectra, and surface compositions consistent with sulfur addition. Density functional theory calculations further show that these observations can be reproduced by a stable graphene episulfide structure in which sulfur bridges two lattice carbon atoms. A decisive control experiment using isotopically pure 13C graphene nevertheless rules out this assignment. Although the intrinsic graphene Raman bands undergo the expected isotope shifts, the characteristic reaction–product bands near 1260 and 1450 cm–1 remain unchanged. The carbon atoms contributing to these modes therefore originate from extrinsic species rather than from the graphene lattice. Detection of similar products on hexagonal boron nitride further supports the formation of organosulfur species in the gas phase, followed by their selective deposition on hydrophobic surfaces. These results show that an extensive agreement among conventional characterization methods and theoretical predictions can still lead to an incorrect structural assignment. Isotopically labeled graphene provides a direct and broadly applicable control for establishing whether carbon atoms in proposed functional groups originate from the graphitic lattice.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"23 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368349","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0