The Journal of Physical Chemistry Letters最新文献

{"title":"A High-Density Supercritical Fluid of H2","authors":"Atsuko Nakayama,&nbsp;Naoto Fujii,&nbsp;Koji Hirama,&nbsp;Kentaro Hamada,&nbsp;Katsuya Shimizu,&nbsp;Yuki Nakamoto,&nbsp;Satoshi Nakano,&nbsp;Saori Kawaguchi-Imada,&nbsp;Yuichi Akahama,&nbsp;Ayako Ohmura","doi":"10.1021/acs.jpclett.6c02439","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02439","url":null,"abstract":"<p>This study aimed to elucidate the structural evolutionof supercriticalfluid hydrogen (SCF H₂) under high pressure. X-ray diffractionwas performed on SCF H₂ using synchrotron radiation atroom temperature. The structure factor <em>S</em>(<em>Q</em>) was observed in a low-<em>Q</em> region at eachpressure, revealing a crossover at around 0.56 GPa, consistent withour previous Raman spectroscopy results. The average volume per moleculewas calculated at each pressure using the center-to-center distancebetween the nearest neighboring H₂ molecules, reflectingvan der Waals interactions and compression of the internuclear distance.The volumes calculated from the face-centered cubic model were consistentwith those derived from the cited equation of state, with a slightdiscrepancy that increased gradually with the pressure. This findingindicates that further densification following the crossover occursprimarily by intra-atomic/molecular mechanisms rather than intermolecularshortening of distances, which cannot be adequately explained by theclose-packed coordination model alone.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11754–11759"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149188021","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}

{"title":"Interfacial Cations Modulate CO2 Reduction Selectivity by Shaping Hydrogen-Bond Networks and Water Orientation","authors":"Hang Wang,&nbsp;Yuan Liang,&nbsp;Chuanjun Wang,&nbsp;Haomiao Cao,&nbsp;Qiang Liao,&nbsp;Yang Wang,&nbsp;Qian Fu,&nbsp;Xun Zhu","doi":"10.1021/acs.jpclett.6c02653","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02653","url":null,"abstract":"<p>Electrochemical CO₂ reduction (ECR) is highlysensitiveto the electrode-electrolyte interfacial microenvironment (EEIM).However, how the hydration structures of alkali-metal cations reorganizeEEIM and thereby influence the energetics of ECR and hydrogen evolutionreaction (HER) related elementary steps remains unclear. Here, explicit-solvent <em>ab initio</em> molecular dynamics simulations were used to elucidatethe cation-dependent restructuring of interfacial water. Specifically,cation-specific hydration governs the spatial distribution, hydrogen-bondconnectivity, and orientation of interfacial water. Strongly hydratedLi⁺ maintains a highly connected hydrogen-bond network,lowers the activation barrier for Volmer water activation, and facilitatesthe removal of the generated OH^– from the interface.In contrast, weakly hydrated K⁺ creates a broader water-depletionregion near the electrode, disrupts hydrogen-bond connectivity, andpromotes a more pronounced H-down orientation of interfacial water.This reconstructed interface increases the accessibility of waterhydrogen atoms to adsorbed *CO₂, thereby creating an EEIMthat favors ECR. Moreover, weakly hydrogen-bonded, K⁺ coordinatedwater provides a more energetically favorable proton-donation environmentthan water embedded in a strongly connected hydrogen-bond network,thereby lowering the activation barrier for *COOH formation. Thesefindings establish a molecular-level link among cation hydration strength,interfacial water restructuring, and reaction selectivity, providinga mechanistic basis for tuning electrochemical interfacial microenvironmentsthrough cation engineering.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11947–11954"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173581","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}

{"title":"Decoding Defect-Driven Ultrafast and Nonlinear Optical Properties of MoS2 Nanocracks","authors":"Sajal Rai,&nbsp;Sanyam Jain,&nbsp;Ravi Dutt,&nbsp;Anshu Kumar Singh,&nbsp;Rajiv K. Singh,&nbsp;Anchal Srivastava","doi":"10.1021/acs.jpclett.6c02406","DOIUrl":"10.1021/acs.jpclett.6c02406","url":null,"abstract":"<p>Ultrafastspectroscopic techniques have emerged as powerfultoolsfor unravelling the fundamental carrier dynamics, charge transfer,and excitonic interactions in low-dimensional materials. Among these,two-dimensional transition metal dichalcogenides (TMDs) such as molybdenumdisulfide (MoS₂) exhibit remarkable light–mattercoupling and nonlinear optical (NLO) behavior. However, most previousinvestigations have primarily focused on intrinsic excitonic processes,often overlooking the critical influence of structural imperfectionssuch as defect-, grain boundary-, and nanocrack-driven inhomogeneitiesthat naturally arise during synthesis and afterward. These imperfectionsdrastically modify charge transfer pathways and exciton relaxation,thereby altering the material’s nonlinear optical response.In the present work, MoS₂ thin films were synthesized viaatmospheric pressure chemical vapor deposition (APCVD) and were subjectedto ultrafast transient absorption (UTA) spectroscopy, revealing adistinct subpicosecond relaxation component, attributed to eitherself-trapped exciton (STE) formation or highly efficient energy funnelingat defect-rich regions. This process occurs on a time scale fasterthan the typical exciton-trapping time (τ₁) reportedfor MoS₂, indicating nearly instantaneous exciton localizationand transfer within the crystal lattice. A strain-dependent analysiswas also carried out to correlate the lattice deformation with theobserved charge-carrier dynamics with an estimated strain potentialof <em>D</em> ≈ 0.295 eV. Apart from this, open- andclosed-aperture Z-scan measurements demonstrated strong third-ordernonlinearity, dominated by two-photon absorption (TPA) and self-defocusingeffects. The calculated nonlinear parameter absorption coefficient(β), 2.22 × 10^–15 m/W, refractive index(<em>η₂</em>), −1.17 × 10^–12 m²/W, and third-order susceptibility(χ³), 1.91 × 10^–12 esu, confirma robust defect-assisted nonlinearity in the system. These findingsestablish a direct correlation between structural integrity, defect-mediatedexciton dynamics, and nonlinear optical response in APCVD-grown MoS₂, offering new insights into the design of ultrafast photonicand optoelectronic devices based on two-dimensional materials.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11854–11862"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049570","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}

{"title":"Attacking Bridging Sulfur by a Soft Cation to Disrupt Lithium Polysulfide Clusters for Low-Temperature Lithium–Sulfur Batteries","authors":"Jin-Hao Zhang,&nbsp;Xiao-Zhong Fan,&nbsp;Yu Zhang,&nbsp;Xiao-He Zhou,&nbsp;Yu-Kun Wang,&nbsp;Na Du,&nbsp;Chen-Hao Yu,&nbsp;Wen-Long Cai,&nbsp;Long Kong","doi":"10.1021/acs.jpclett.6c03037","DOIUrl":"10.1021/acs.jpclett.6c03037","url":null,"abstract":"<p>Low-temperature-induced rigid and cage-like lithium polysulfideclusters impede the kinetics of sulfur (S) conversion. Electronicanalysis reveals a charge density contrast within these structures,in which terminal S with high charge density serves as a “hardbase” to tightly bind with Li⁺, while the bridgingS featuring low charge density acts as a “soft base”.This soft base would be the ideal site for lithiation-incurred bondcleavage due to low bond energy. How to further loosen the bridgingS–S bond and facilitate Li attack in these sites has not beenstudied. Guided by hard–soft-acid–base (HSAB) principles,this work proposes large-radius Cs⁺ as a “soft Lewisacid” (with respect to Li⁺) to selectively targetsoft bridging S sites, aiming at disrupting LiPS cluster symmetryand reducing the Mulliken bond order of bridging S–S, effectivelylowering the rate-determining lithiation barrier. This work highlightslarge-cation-mediated structural disruption as a unique strategy toregulate specific S bond cleavage for expediting lithium–sulfurbattery conversion kinetics at low temperature.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11981–11987"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092059","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}

{"title":"Polymer-Linked\u0000Nanoparticle Networks Running on Heat\u0000Can Act as Computing Devices","authors":"Xingfei Wei,Manuel Palma Banos,Rigoberto Hernandez","doi":"10.1021/acs.jpclett.6c02829","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02829","url":null,"abstract":"Abstract Developing physical neural network (PNN) hardwares is important to next-generation artificial intelligence systems. Phononic devices─using heat current to encode and process information─is one of the solutions to neuromorphic computing. In this work, we backmap an artificial neural network (ANN) into a PNN simulation model using polymer networked nanoparticles (PNNPs). Our atomistic simulation results demonstrate that the polymer-linked nanoparticle networks can potentially realize information processing─viz., classification of input temperatures according to the output heat currents. Using high-throughput molecular dynamics (MD) simulations and the trust region Bayesian optimization (TuRBO) methods, we tune the plasticity of polymer linkers and the temperatures of nanoparticles─28 parameters in total─to optimize the performance of the PNNP machines, which is analogous to tuning of the weights and bias of the corresponding ANNs. After five rounds of high-throughput MD simulations, we demonstrate that the PNNP machine can better label different input temperatures, and thus its performance is improved. We also use a testing data set to verify the heat flow outputs from the top five PNNP machines in each round.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"11 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209837","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}

{"title":"Structural Fluctuation in Liquids Revealed by High-Order\u0000Harmonic Generation","authors":"Tiantian Tong,Xiaowei Ren,Jie Hu,Guoqiang Tang,Shan Xi Tian","doi":"10.1021/acs.jpclett.6c02160","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02160","url":null,"abstract":"Abstract High-order harmonic generation (HHG) in liquids has attracted considerable attention, yet the fundamental processes responsible for the liquid-related differences are still not well elucidated. Here we systematically investigate the liquid-HHG spectra of water, acetonitrile, methanol, ethanol, and 1- and 2-propanols. Within the framework of the three-step recollision model, we extract the values of maximum excursion length (Lmax) of the electron prior to its recapture. We establish a phenomenological scaling law linking the experimental Lmax values to the liquid properties (viscosity, mass density, and molecular thermal speed), exhibiting an intrinsic connection between the HHG spectra and structural fluctuations within liquids. This relationship is further validated through a quantitative comparison of the macroscopic self-diffusion coefficients of the liquids. Our findings also indicate that HHG spectroscopy emerges as a promising tool for probing liquid properties.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"22 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209840","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}

{"title":"Correlating In Situ Growth Kinetics with Nanorod Morphology Using iSCAT-FlucCS","authors":"Ruchir Gupta,&nbsp;Shubham Mulay,&nbsp;Sachin Dev Verma","doi":"10.1021/acs.jpclett.6c02895","DOIUrl":"10.1021/acs.jpclett.6c02895","url":null,"abstract":"<p>Anisotropic growth in seed-mediated nanocrystal synthesisdependson nucleation and autocatalytic growth, and the aspect ratio is expectedto be related to the ratio of growth to nucleation rates. Direct kineticevidence for this link is limited, because it is difficult to measureboth kinetics and morphology in the same experiment. In this work,we examined the growth kinetics of seed-mediated silver nanorods andlinked them to their shapes using a dual-mode platform, iSCAT-FlucCS.We measured nucleation (<em>k</em>₁) and growth(<em>k</em>₂) kinetic parameters in situ with wide-fieldiSCAT microscopy and compared them to nanorod dimensions obtainedfrom iSCAT fluctuation correlation spectroscopy. We found that <em>k</em>₂ increased with seed concentration, and <em>k</em>₁ shows no clear monotonic dependence on seedvolume, modestly high at low seed levels. The nanorod aspect ratiodecreased as <em>k</em>₂/<em>k</em>₁ rose above a certain point, suggesting a shift from seed-limitedto monomer-limited growth, with more variability below this threshold.These findings provide direct kinetic evidence that competition betweennucleation and growth shapes seed-dependent nanorod anisotropy.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11809–11815"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090902","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}

{"title":"Phenylammonium Grafted SAM Molecule in Molecule-Extrusion Process to Enhance Perovskite Film Quality and Interfacial Passivation","authors":"Jinfeng Huang,&nbsp;Chuanxin Chen,&nbsp;Jin-Long Wang,&nbsp;Xiao Yang,&nbsp;Siyuan Tang,&nbsp;Jiacheng He,&nbsp;Chao Sun,&nbsp;Haojie Chen,&nbsp;Huiyi Zhang,&nbsp;Rui Hu,&nbsp;Beibei Zong,&nbsp;Zhubing He","doi":"10.1021/acs.jpclett.6c02870","DOIUrl":"10.1021/acs.jpclett.6c02870","url":null,"abstract":"<p>Widely used as hole transport layers (HTLs) for invertedperovskitesolar cells (PSCs), the functions of phosphonic acid-based self-assemblymonolayer (SAM) molecules in the bulk of the perovskite film havebeen studied in a limited manner but are essential. In this work,we designed a phenylammonium-functionalized SAM molecule termed 4PACDto study its effect on the perovskite crystal growth and the interfacialdefect state passivation in the bulk of the perovskite film, dependingon the molecule-extrusion process. By means of in situ photoluminescence,a slower crystal growth pathway was evidenced for 4PACD-incorporatedperovskite film with much improved quality, which cuts down the defectdensity by nearly one order. Finally, the incorporation of 4PACD resultedin a champion device power conversion efficiency (PCE) of 26.78% comparedwith 25.01% for the control device with 4PACD as the HTL. The targetdevice can reserve 98.9% of the initial PCE after 1000 h of lightsoaking, while the control retained 88.7%. This work highlights theperovskite growth advantage of the SAM incorporated in the bulk ofthe perovskite film over using it only as HTL, demonstrating the greatpotential of the molecule-extrusion process for high-performance PSCswithout predepositing HTLs.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11971–11980"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091534","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}

{"title":"In Operando Raman Reveals Voltage-Driven SEI Chemistry in Fluorinated Gel Electrolytes","authors":"Rhyz Pereira,&nbsp;Andrew Dopilka,&nbsp;Subhadra Jamkar,&nbsp;Jantakan Nedsaengtip,&nbsp;Taber Yim,&nbsp;Robert Kostecki,&nbsp;Vibha Kalra","doi":"10.1021/acs.jpclett.6c02566","DOIUrl":"10.1021/acs.jpclett.6c02566","url":null,"abstract":"<p>A particular advantage of gel polymer electrolytes (GPEs)has beentheir ability to incorporate chemical moieties that create stableelectrode–electrolyte interfaces that guide uniform depositionand stripping of lithium. Understanding the chemical dynamics at theseinterfaces remains challenging. Previously, we reported that polyvinylidenefluoride-cohexafluoropropylene (PVDF-HFP) GPEs with anether cosolvent showed greater stability in lithium metal symmetriccells. In this work, we used a Cu|PVDF-HFP|Li cell design along within operando Raman spectroscopy to conduct a thorough characterizationof the electrolyte–electrode interface to observe the chemicaldynamics at work during electrode polarization, lithium plating, andstripping. We observe that PVDF-HFP, cosolvent, and supporting saltall contribute to the initial SEI formation prior to plating. Thespectral and electrochemical data using this method allow us to understandthe contribution of different chemical species in the evolution ofinterfaces in lithium metal batteries.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11963–11970"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090987","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}

{"title":"Decoupling Electron and Hole Injection Dynamics in Colloidal Nanocrystals via Potentiostatic Polarization Spectroelectrochemistry","authors":"Junkai Wang,&nbsp;Huichao Zhang,&nbsp;Bo Huang,&nbsp;Chenyu Du,&nbsp;Shiji Chen","doi":"10.1021/acs.jpclett.6c02515","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02515","url":null,"abstract":"<p>The outstanding optoelectronic potential of colloidalnanocrystalshas driven intensive study of their charge carrier behavior. However,conventional spectroelectrochemistry (SEC) may yield results thatdeviate from practical device operation because it typically relieson gradual potential scans. Here, we investigate mixed-phase and purewurtzite CdSe/CdS core/shell nanocrystals using potentiostatic polarizationSEC. Mixed-phase nanocrystals exhibit spectral recovery under bothbiases, originating from self-elimination of excess electrons (negativebias) and photo-assisted elimination of trap states, whose rapid charging/discharginginduces local electric field fluctuations that cause asymmetric spectralbroadening (positive bias). In contrast, pure wurtzite nanocrystalsallow additional hole injection, causing a reversible spectral blueshift.Under negative bias, they exhibit slow photoluminescence quenchingand redshift from gradual electron injection. These differences stemfrom the lack of conduction band intermediate levels and a valenceband barrier due to zinc blende stacking faults, suggesting microstructuralengineering may enable balanced carrier injection.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11869–11877"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173936","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}