The Journal of Physical Chemistry Letters最新文献

{"title":"Understanding the Selectivity Differences of NO Electroreduction on Ag and Au Electrodes","authors":"Lin Li, Dong Luan, Jun Long, Jianping Xiao","doi":"10.1021/acs.jpclett.5c00656","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00656","url":null,"abstract":"Although noble metals Ag and Au have similar chemical reactivities, their catalytic selectivity for NO electroreduction is significantly different. Namely, hydroxylamine is often considerably produced on Ag while not observed on the Au electrode. In this study, first-principles calculations and the electric field controlling constant potential (EFC–CP) method are adopted to unveil the underlying reasons. We first reveal a distinct NO* adsorption configuration, vertical on Ag and inclined on Au, leading to different reduction pathways to NOH* and HNO*, respectively. Via complete electrochemical barrier calculations and detailed kinetic analysis, we find the hydroxylamine selectivity difference between Ag and Au is mainly induced by adsorption strength of NH₂OH*. On Ag, the obtained NH₂OH* prefers to desorb and produce hydroxylamine, while NH₂OH* is bonded strongly to Au and favors further reduction to ammonia. The study advances our understanding of factors regulating product selectivity, providing crucial insights for designing NO electroreduction catalysts toward hydroxylamine production.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"30 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723616","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":"Boosting Photovoltaic Efficiency: The Role of Longitudinal Carrier Transport in Carbon Dot-Modified Perovskite Films","authors":"Xinlei Zhang, Jing Leng, Shengli Zhao, Qing Yang, Peng Xu, Shiqi Rong, Yan Xu, Wenming Tian, Shengye Jin","doi":"10.1021/acs.jpclett.5c00637","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00637","url":null,"abstract":"Defect passivation engineering, an effective strategy to optimize grain boundaries and reduce defects in organic–inorganic hybrid perovskites, has been widely used to improve device performance; however, knowledge of its impact on the carrier transport property is still limited. Herein, we take carbon dot (CD) passivation as an example to explore the effect of surface modification on the longitudinal carrier diffusivity (D) in CH₃NH₃PbI₃ perovskite films by using transient reflection spectroscopy. The results show that the D value remarkably increases from 0.30 cm² s^–1 in unmodified film to 1.02 cm² s^–1 in CD-modified film due to their enhanced conductivity, where CDs act as a highly conductive interstitial medium to enhance intergrain contact. Benefiting from the increase in carrier diffusivity, the power conversion efficiency of CD-modified perovskite solar cells (PSCs) increased from 23.1% (unmodified) to 25.4%, strongly confirming the positive effect of CD passivation on the PSC performance. Our finding highlights a novel avenue for enhancing PSC performance through the improvement of longitudinal carrier diffusivity via high-conductivity nanomaterial doping.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"215 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723615","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":"Control of Heat Flow in a Soft Matter: Anisotropic Heat Transport in a Discotic Columnar Liquid Crystal Capable of Reversible Alignment Switching","authors":"Meguya Ryu, Ryosuke Takehara, Shuji Kamegaki, Hiromichi Yokoyama, Takashi Kajitani, Junko Morikawa, Takanori Fukushima","doi":"10.1021/acs.jpclett.5c00354","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00354","url":null,"abstract":"Discotic columnar liquid crystals (LCs) hold promise as thermal interface materials that allow heat to flow preferentially in the desired direction, whereas their heat transport properties remain elusive, particularly in terms of anisotropy related to their columnar alignments. Using a discotic columnar LC (TPC₄F₆) that allows for complete alignment control by applying mechanical shear, we investigated the alignment dependence of the thermal diffusivity using a dedicated setup for micro temperature wave analysis. We found that the thermal diffusivity in the direction perpendicular to the columns is larger, compared with the direction along the columns. Interestingly, this trend is opposite to that observed for a single crystal system composed of an identical aromatic core motif. This result demonstrates that the anisotropy of heat transport can change depending on the phases of materials even when they have similar compositions, providing insights into the design of organic materials for thermal management.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"131 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734472","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":"Excitonic Fano Scattering Behaviors of Carbon Nanotubes from Interference with Dispersant","authors":"Seongjoo Hwang, In-Seung Choi, Sang-Yong Ju","doi":"10.1021/acs.jpclett.5c00319","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00319","url":null,"abstract":"Rayleigh scattering behavior of single-walled carbon nanotubes (SWNTs) has been instrumental in understanding their exciton behaviors, but their bulk scattering interactions with molecules in dispersion remain unexplored. Here, we found the excitonic Fano scattering behaviors in interfering dispersant-wrapped SWNT dispersions and characterized them both experimentally and theoretically. Using an integrating sphere, we differentiated scattering spectra from extinction and absorption spectra at both single-chirality and ensemble levels. The scattering spectra revealed asymmetric excitonic and exciton–phonon bands contrasting Lorentzian shapes from noninterfering dispersant-wrapped SWNT. A scattering cross-sectional equation, derived from Fano resonance theory and incorporating the dielectric constants of SWNT and its environment, successfully simulates the experimental result. The analysis underscored the impact of the surrounding molecules on the excitonic interactions, with significant implications for the optoelectronic properties of SWNTs. The findings suggest potential applications of SWNTs in sensory and modulator schemes, where the optoelectronic response of nanomaterials is tuned by selection of molecules.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"2 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723614","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":"Chemical Mapping of Supramolecular Self-Assembled Monolayers via Atomic Force Microscopy-Based Infrared with a Nanometer-Scale Lateral Resolution","authors":"Alexandre Dazzi, Frank Palmino, Ariane Deniset-Besseau, Jérémie Mathurin, Vincent Luzet, Peter De Wolf, Qichi Hu, Chunzeng Li, Cassandra Phillips, Frédéric Chérioux","doi":"10.1021/acs.jpclett.5c00360","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00360","url":null,"abstract":"Atomic force microscopy-based infrared (AFM-IR) techniques have long enabled chemical imaging of surfaces with spatial resolutions down to 10 nm. In this study, we push the boundaries of AFM-IR spatial resolution to the single-nanometer scale, achieving chemical mapping of supramolecular networks at the submolecular level. This breakthrough is made possible by implementing an innovative tapping-mode AFM-IR approach. Such unprecedented resolution opens new horizons for advancements in nanoscience.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"39 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723617","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":"Zero Phonon Line and Near-Infrared Luminescence in Cs4CdSb2–xCrxCl12 Quadruple-Layered Halide Double Perovskite","authors":"Tiasha Roy, Bhyrappa Puttaiah, Chandran Sudakar","doi":"10.1021/acs.jpclett.4c03246","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03246","url":null,"abstract":"There is growing interest in understanding the optoelectronic properties of inorganic lead-free layered halide double perovskites (LHDPs). Here, we report a distinctive sharp zero phonon line (ZPL) emission at 727 nm and an intense, broad near-infrared (NIR) emission at 757 nm from the photoluminescence (PL) spectra measured at temperatures below 217 K, resulting from Cr³⁺ substitution in Cs₄CdSb₂Cl₁₂ LHDPs. Pristine Cs₄CdSb₂Cl₁₂ exhibits only a weak and broad self-trapped excitonic emission centered around 590 nm. On the contrary, an NIR emission (fwhm = 72.5 nm) at 757 nm is also observed at 300 K in Cs₄CdSb_2–<i>x</i>Cr_<i>x</i>Cl₁₂ (<i>x</i> = 0.05 to 0.3) originating from the <i>d</i>–<i>d</i> transition of Cr³⁺ ions. This broad mode evolves into 2 distinct emissions: a ZPL (at 727 nm) and an intense, broad NIR (at 746 nm) sideband below 217 K. The ZPL originates from the spin-allowed ⁴<i>T</i>_2g → ⁴<i>A</i>_2g <i>d</i>–<i>d</i> transition from Cr³⁺. ZPL intensity increases with Cr³⁺ substitution. This study demonstrates the promising optical properties of Cr³⁺-substituted LHDPs, indicating their potential for future applications in optoelectronic devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"61 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713762","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":"Correction to “Remarkable Insensitivity of Protein Diffusion to Protein Charge”","authors":"Setare Mostajabi Sarhangi, Dmitry V. Matyushov","doi":"10.1021/acs.jpclett.5c00663","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00663","url":null,"abstract":"Calculations of diffusion constants from molecular dynamics (MD) simulations require finite-size corrections. (1) The diffusion constant &lt;i&gt;D&lt;/i&gt;&lt;sub&gt;MD&lt;/sub&gt; calculated with periodic boundary conditions (PBC) employed in MD needs correction for hydrodynamic effects of viscous solvent flow within the lattice of periodically replicated images of the tagged diffusive particle. For a cubic simulation box of length &lt;i&gt;L&lt;/i&gt;, one obtains the diffusion constant of the infinite system &lt;i&gt;D&lt;/i&gt; from the PBC value &lt;i&gt;D&lt;/i&gt;&lt;sub&gt;MD&lt;/sub&gt; according to the following equation. (1) We have recently reported MD simulations of the diffusion constants of two proteins, green fluorescent protein (GFP) and plastocyanin (PC), in TIP3P water. (3) The finite-size term in eq 1 was incorrectly calculated, and the corrected &lt;i&gt;D&lt;/i&gt; values in Table 2 of ref (3) were close to the MD values &lt;i&gt;D&lt;/i&gt;&lt;sub&gt;MD&lt;/sub&gt;. When we re-examined the reported values, we noticed that &lt;i&gt;D&lt;/i&gt; ≃ 257 μm&lt;sup&gt;2&lt;/sup&gt;/s from eq 1 significantly exceeds &lt;i&gt;D&lt;/i&gt;&lt;sub&gt;MD&lt;/sub&gt; ≃ 20.8 μm&lt;sup&gt;2&lt;/sup&gt;/s for the system size of &lt;i&gt;L&lt;/i&gt; ≃ 86 Å (≃18,000 TIP3P water molecules). The finite-size correction, ≃236 μm&lt;sup&gt;2&lt;/sup&gt;/s, is thus significantly higher than the MD result itself (η = 0.306 cP for TIP3P water (4) was applied in eq 1). Given approximations involved in deriving the correction term, (1) this observation puts under doubt the validity of &lt;i&gt;D&lt;/i&gt; calculated according to eq 1. Here, we present additional data from MD simulations of GFP and PC diffusion in simulation boxes of different size to show that eq 1 highly overestimates &lt;i&gt;D&lt;/i&gt;(&lt;i&gt;L&lt;/i&gt;) (Figure 1 and Table 1). The MD simulation protocol follows ref (3), with modifications to the box size and the number of water molecules. From charge mutants studied in ref (3), only the wild-type GFP with a charge of −6 is considered here. PC is in its reduced state with the charge of −9. We find strongly divergent values of &lt;i&gt;D&lt;/i&gt;(&lt;i&gt;L&lt;/i&gt;) and &lt;i&gt;D&lt;/i&gt;&lt;sub&gt;MD&lt;/sub&gt;(&lt;i&gt;L&lt;/i&gt;) (Figure 1), while extrapolation to &lt;i&gt;L&lt;/i&gt;&lt;sup&gt;–1&lt;/sup&gt; → 0 gives consistent results for &lt;i&gt;D&lt;/i&gt;(∞) and &lt;i&gt;D&lt;/i&gt;&lt;sub&gt;MD&lt;/sub&gt;(∞) (black dots in Figure 1). Figure 1. &lt;i&gt;D&lt;/i&gt;&lt;sub&gt;MD&lt;/sub&gt;(&lt;i&gt;L&lt;/i&gt;) (blue) and size-corrected &lt;i&gt;D&lt;/i&gt;(&lt;i&gt;L&lt;/i&gt;) (red, eq 1) vs &lt;i&gt;L&lt;/i&gt;&lt;sup&gt;–1&lt;/sup&gt; for GFP and PC proteins. The solid lines are linear fits of the MD results (points). The black dots indicate crossing of two interpolations to the infinite-size limit &lt;i&gt;L&lt;/i&gt;&lt;sup&gt;–1&lt;/sup&gt; → 0. Equilibrium trajectories for 50 ns, with dynamics calculated from 10 ns trajectories with the integration time of 1 fs and saving time of 5 fs. Same simulation parameters for PC, except for 100 ns equilibration trajectories. Variations between &lt;i&gt;D&lt;/i&gt;&lt;sub&gt;&lt;i&gt;F&lt;/i&gt;&lt;/sub&gt;(&lt;i&gt;L&lt;/i&gt;) data points are caused by corresponding variations in the force variance since τ&lt;sub&gt;&lt;i&gt;m&lt;/i&gt;&lt;/sub&gt; is independent of &lt;i&gt;L&lt;/i&gt;. &lt;i&gt;D&lt;/i&gt;&lt;sub&gt;&lt;i&gt;F&lt;/i&gt;&lt;/sub&gt; refers to eq 2. We have also calculated diffusion constants from the dynamic","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"34 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713767","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":"Ultrafast Dynamics and Rearrangement of the EUV Photoacid Generator Phenyl Triflate","authors":"Sung Kwon,&nbsp;Jacob Stamm and Marcos Dantus*,&nbsp;","doi":"10.1021/acs.jpclett.4c0362110.1021/acs.jpclett.4c03621","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03621https://doi.org/10.1021/acs.jpclett.4c03621","url":null,"abstract":"<p >Extreme UV photolithography is a high-energy process crucial for modern computer chip fabrication, where photoacid generators (PAGs) enhance radiation exposure by producing reactive chemical species. This study investigates the ultrafast dissociative dynamics of phenyl triflate, a widely used PAG, under high-energy ionizing conditions. The dissociative ionization of the phenyl triflate cation, which includes a molecular rearrangement that releases SO₂ and forms the phenyl trifluoromethyl ether cation, is measured over the first 5 ps. These dynamics reveal vibrational coherence corresponding to a torsional mode of the cation, involving the twisting of the phenyl group into the O–S–C plane. Electronic structure calculations for the radical cation are in good agreement with the experimentally observed vibrational coherence. These findings provide valuable insights into the behavior of phenyl triflate under ionizing conditions similar to its industrial usage.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 13","pages":"3397–3401 3397–3401"},"PeriodicalIF":4.8,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpclett.4c03621","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758843","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ultrafast Dynamics and Rearrangement of the EUV Photoacid Generator Phenyl Triflate","authors":"Sung Kwon, Jacob Stamm, Marcos Dantus","doi":"10.1021/acs.jpclett.4c03621","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03621","url":null,"abstract":"Extreme UV photolithography is a high-energy process crucial for modern computer chip fabrication, where photoacid generators (PAGs) enhance radiation exposure by producing reactive chemical species. This study investigates the ultrafast dissociative dynamics of phenyl triflate, a widely used PAG, under high-energy ionizing conditions. The dissociative ionization of the phenyl triflate cation, which includes a molecular rearrangement that releases SO₂ and forms the phenyl trifluoromethyl ether cation, is measured over the first 5 ps. These dynamics reveal vibrational coherence corresponding to a torsional mode of the cation, involving the twisting of the phenyl group into the O–S–C plane. Electronic structure calculations for the radical cation are in good agreement with the experimentally observed vibrational coherence. These findings provide valuable insights into the behavior of phenyl triflate under ionizing conditions similar to its industrial usage.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"10 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713443","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":"Perspectives on the Dynamic Nuclear Polarization Mechanisms of Monoradicals: Overhauser Effect or Thermal Mixing?","authors":"Frédéric A. Perras, Frédéric Mentink-Vigier, Svetlana Pylaeva","doi":"10.1021/acs.jpclett.5c00225","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00225","url":null,"abstract":"This mini-review summarizes the evolving debate regarding the origins of the absorptive features seen in the dynamic nuclear polarization (DNP) spectra of certain monoradicals when they are irradiated at their electron Larmor frequency. This feature has drawn attention due to its reverse scaling with respect to the magnetic field strength and potential for high-field DNP. Two competing hypotheses have been introduced to explain the DNP feature based on (1) the Overhauser effect and low-temperature molecular dynamics and (2) radical clustering and a thermal mixing mechanism. Since the original discovery, a large number of experimental observations have been made in attempts to understand and ultimately leverage the mechanism. We summarize these observations and provide critical assessments of how the competing hypotheses approach them.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"57 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713764","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}