Physical Chemistry Chemical Physics最新文献

{"title":"Probing polymer effects on interfacial Li-ion transport in hybrid solid electrolytes: LLZO–PCL compared with LLZO–PEO","authors":"Gourav Shukla,Melania Kozdra,Laura Hoelzer,Diddo Diddens,Andreas Heuer","doi":"10.1039/d6cp02019d","DOIUrl":"https://doi.org/10.1039/d6cp02019d","url":null,"abstract":"Hybrid polymer–ceramic electrolytes are promising candidates for solid-state lithium-ion batteries, yet ion transport at polymer–ceramic interfaces often limits performance. Atomistic molecular dynamics simulations at elevated temperatures are used to investigate {color{black} differences in $rm Li^{+}$ transport between PCL- and PEO-based polymer–ceramic interfaces}. The investigated interface is built of $rm Li_7La_3Zr_2O_{12}$ (LLZO) ceramic and poly($rm varepsilon$-caprolactone) (PCL) polymer doped with bis(trifluoromethanesulfonyl)imide (LiTFSI) (LLZO–PCL), and a direct comparison is established with an analogous interface composed of LiTFSI-doped poly(ethylene oxide) (PEO) and LLZO (LLZO–PEO). The LLZO–PCL interface exhibits pronounced interfacial structuring, including strong adsorption of hydroxyl oxygen atoms at the ceramic surface. $rm Li^{+}$ transfer across the interface is quantified from transition statistics and analyzed using free-energy profiles. Remarkably, LLZO–PCL exhibits an approximately 35-fold larger phase-exchange barrier (PEB) rate than LLZO–PEO, primarily due to a significantly lower PEB height for polymer–ceramic transfer. Analysis within the framework of overdamped Kramers theory indicates strongly damped interfacial dynamics and suggests spatially heterogeneous friction along the reaction coordinate. Overall, the results demonstrate that {color{black} the substantially different interfacial $rm Li^{+}$ transfer in PCL and PEO is mainly associated with differences in the PEB height}. Our previously developed multiscale framework is used to evaluate which {color{black} of the two polymer systems} is more likely to enhance the overall conductivity in hybrid solid electrolytes by facilitating $rm Li^{+}$ transport through the fast ceramic phase. Finally, effective Li–polymer coordination strength and polymer adhesion at the ceramic surface emerge as key factors governing interfacial ion transport and the efficient utilization of ceramic transport pathways in hybrid solid electrolytes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"6 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173158","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":"Polarization-insensitive near-infrared quasi-BIC perfect absorbers realized <i>via</i> Brillouin zone folding and temporal coupled-mode theory.","authors":"Mousu Wan, Yihao Tang, Mingli Sun, Xiaogang Wang, Tingting Sun, Bijun Xu","doi":"10.1039/d6cp03014a","DOIUrl":"10.1039/d6cp03014a","url":null,"abstract":"<p><p>We present a high-<i>Q</i> near-infrared metasurface absorber enabled <i>via</i> Brillouin zone folding (BZF) modulated bound states in the continuum (BIC). The structure comprises an array of asymmetric silicon hole-pillar nanocylinders, a SiO₂ spacer layer and a gold reflector. Full-wave simulations based on the finite element method (FEM) are carried out to explore its optical properties. Structural symmetry breaking excites quasi-BIC modes, which feature strong field localization and ultra-narrow resonant bandwidth. Numerical results demonstrate that the proposed device achieves an absorption efficiency of 99.98% at 1154.2 nm, with a <i>Q</i> factor reaching 1170.11. Multipolar decomposition verifies that the resonance is predominantly governed by the toroidal dipole (TD) mode, while the electric dipole (ED) acts as an auxiliary component. We also systematically discuss how lattice period, silicon height, polarization angle and incident angle affect the absorption performance. Temporal coupled-mode theory (TCMT) is employed to fit the spectra and validate the resonant mechanism of quasi-BIC. This work offers an effective design scheme for high-<i>Q</i> narrowband absorbers, which has great application potential in optical sensing and photodetection.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":"24607-24614"},"PeriodicalIF":3.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149056593","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":"Doping polaron analysis","authors":"M. Rasteh,S. M. Azami","doi":"10.1039/d5cp05034k","DOIUrl":"https://doi.org/10.1039/d5cp05034k","url":null,"abstract":"Doping polaron analysis is introduced to analyze charge reorganization driven by the doping process. Eigenanalysis of doping deformation density is presented to identify the doping mechanism and quantify the total number of electron displacements induced by the doping. The formalism is applied to C60 fullerene, where four carbon atoms of fullerene are replaced by boron and nitrogen atoms in different configurations, and the results show that the magnitude of doping charge displacement is governed by boron and nitrogen distance. Three types of doping charge displacement mechanisms are also introduced with respect to eigenpolarons of the doping deformation density matrix.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"232 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152774","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":"Solid-state NMR dipolar recoupling in the presence of large chemical shielding anisotropies by quaternion-based effective Hamiltonian optimal control.","authors":"E Baligács, N Wili, J P Carvalho, A B Nielsen, N C Nielsen","doi":"10.1039/d6cp02762h","DOIUrl":"https://doi.org/10.1039/d6cp02762h","url":null,"abstract":"<p><p>Dipolar recoupling is a key element in magic-angle-spinning (MAS) solid-state NMR spectroscopy with reintroduced dipole-dipole coupling interactions providing information about internuclear distances and enabling transfer of polarization between spins in resolution-enhancing multiple-dimensional experiments. Such methods may be challenged in many important applications by the presence of large anisotropic nuclear spin interactions such as chemical shielding anisotropy. In this paper, we address this challenge by presenting quaternion-based optimal control. This is founded in single-spin operations enabling optimization of effective Hamiltonians with reduced influences from anisotropic shielding. Along with the principles underlying such optimizations, we present numerical and experimental demonstration of ¹⁹F to ¹³C polarization transfer in the presence of ¹⁹F chemical shielding anisotropy.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149178026","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":"Interplay between exchange kinetics, molecular dynamics and polarisation transfer in SABRE hyperpolarisation","authors":"Nazmul Hossain,Joni Eronen,Vladimir V. Zhivonitko,Juha Vaara,Anu Maria Kantola","doi":"10.1039/d6cp03264h","DOIUrl":"https://doi.org/10.1039/d6cp03264h","url":null,"abstract":"Signal amplification by reversible exchange (SABRE) is an effective hyperpolarisation technique that enhances nuclear magnetic resonance (NMR) signal by orders of magnitude through transferring spin order from parahydrogen to target nuclei of a substrate without chemically altering the substrates. The efficiency of SABRE hyperpolarisation is influenced by several factors. These include the polarisation transfer rates and mechanisms governed by the nuclear shieldings, as well as the scalar and dipolar couplings between the nuclei. It also depends on the lifetime of the metal complex, where the polarisation transfer occurs, which is determined by the substrate and hydride dissociation rates. In addition, it depends on the nuclear relaxation times defining the lifetime of the polarisation in the free and the complex-bound substrates. In this work, we have used variable-temperature NMR exchange and relaxation experiments, spin dynamics simulations, and quantum-chemical calculations to shed light into the complicated process of SABRE polarisation in four different molecules: pyridine, pyrazine, 3-fluoropyridine, and 3,5-difluoropyridine. With simulations, we have studied the effects of the individual parameters on the polarisation transfer. As a result, we have obtained better understanding of the effect of longitudinal relaxation times on the polarisation transfer process, along with optimal dissociation rates to maximise the polarisation transfer efficiency for 1H, 19F and 15N nuclei of the substrate. Finally, we predict the temperature ranges to achieve such optimal conditions for the studied systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"69 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151975","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":"Correction: Simulation of protein structure using a coarse-grained potential incorporating the backbone dihedral interactions","authors":"Kanika Kole,Abhik Ghosh Moulick,Jaydeb Chakrabarti","doi":"10.1039/d6cp90190e","DOIUrl":"https://doi.org/10.1039/d6cp90190e","url":null,"abstract":"Correction for ‘Simulation of protein structure using a coarse-grained potential incorporating the backbone dihedral interactions’ by Kanika Kole et al., Phys. Chem. Chem. Phys., 2026, 28, 23541–23554, https://doi.org/10.1039/d6cp02188c.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"33 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152773","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":"Carbon nanotube-induced magnetic shielding effects on Xe NMR from equivariant neural networks","authors":"Ouail Zakary,Tiia Jacklin,Perttu Lantto","doi":"10.1039/d6cp03538h","DOIUrl":"https://doi.org/10.1039/d6cp03538h","url":null,"abstract":"Equivariant graph neural networks (EGNNs) have shown success in building efficient and accurate machine learning interatomic potentials (MLIPs) for molecular dynamics (MD) and in enabling the prediction of nuclear magnetic resonance (NMR) parameters in complex systems. In this work, EGNNs are used to fine-tune an atomistic foundation model, which serves as an MLIP for large-scale molecular dynamics simulations of xenon in carbon nanotubes. In addition, EGNNs are employed to develop a machine-learning model for the 129Xe NMR magnetic shielding tensor, σ, enabling its direct prediction from the MLMD snapshots. Both models are data-efficient and remain accurate well beyond their training data. Using this dual-model framework, we show that xenon encapsulated in carbon nanotubes experiences a nanotube-induced, negative 129Xe isotropic chemical shift that varies non-monotonically with nanotube diameter and depends further on temperature and Xe loading, establishing this dual-model approach as an efficient route to interpreting confinement-driven 129Xe NMR response.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152767","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":"Precise Separation and Photoluminescence Enhancement of Hydrophilic Ultrasmall CdTe Nanoparticles","authors":"Ryo Takahata,Masaki Saruyama,Seiji Yamazoe,Toshiharu Teranishi","doi":"10.1039/d6cp03037h","DOIUrl":"https://doi.org/10.1039/d6cp03037h","url":null,"abstract":"Hydrophilic semiconductor nanoparticles (NPs) with sizes of ~2 nm are attractive for sensing applications because their high surface-to-volume ratios enhance their interactions with target species. However, systematic experimental access to this ultrasmall regime remains limited because of the difficulty in isolating uniform NPs. Herein, we employed polyacrylamide gel electrophoresis (PAGE) to precisely separate a series of ultrasmall CdTe NPs. The PAGE-separated CdTe NPs exhibited gradual blue shifts in the excitonic absorption peaks, as is characteristic of colloidal NPs, rather than the discrete peak progression observed in nanoclusters (NCs), while retaining sharp excitonic absorption features that are reminiscent of NCs.These observations indicate that ultrasmall CdTe NPs exhibit optical characteristics of both colloidal NPs and NCs. While excitonic absorption features evolve continuously as the size decreases, the photoluminescence (PL) properties are strongly influenced by the surface and defect states. The PL intensity decreased markedly for smaller CdTe NPs, whereas thermal annealing enhanced the PL efficiency of larger CdTe NPs. These results demonstrate that PAGE fractionation provides practical access to the ultrasmall regime and offers insights into the optical properties at the boundary between NCs and NPs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151979","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":"Hidden excimer formation in the gas-phase photodynamics of a BN-doped phenanthrene","authors":"Jonas Fackelmayer,Michael Bühler,Michael Müller,Holger Helten,Ingo Fischer,Merle I. S. Röhr","doi":"10.1039/d6cp02868c","DOIUrl":"https://doi.org/10.1039/d6cp02868c","url":null,"abstract":"Replacing CC units by isoelectronic BN motifs provides a powerful strategy to tune the electronic structure and excited-state chemistry of polycyclic aromatic hydrocarbons (PAHs). Here, we combine multiphoton ionization spectroscopy, time-resolved photoelectron imaging, ion velocity-map imaging, and quantum-chemical calculations to disentangle the monomer and dimer photophysics of 4a,4b-azaboraphenanthrene. The monomer exhibits a structured S1 ← S0 spectrum with an origin at 22 880 ± 15 cm−1, corresponding to 2.837 eV, and pronounced activity in low-wavenumber deformation modes. Photoelectron spectroscopy yields an adiabatic ionization energy of 7.18 ± 0.02 eV. While the structured spectrum, high fluorescence quantum yield, small computed geometry changes, and weak spin–orbit couplings all point to a long-lived monomer S1 state, time-resolved photoelectron images reveal an additional picosecond component. Ion imaging shows that this component originates from dissociative ionization of the molecular dimer, which projects dimer excited-state dynamics into the monomer mass channel. Computations identify the initially excited dimer state as a bright H-aggregate-like exciton, followed by ultrafast S2 → S1 internal conversion and subsequent structural relaxation toward an excimeric S1 minimum. The experimentally observed ≈15 ps time constant is therefore assigned to excimer formation in the neutral dimer.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152771","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":"Revealing time-regime-dependent defect formation pathways in perovskite single crystals through physics-informed machine learning","authors":"Zimo Liang,Wenlong Dong,Yucheng Yang,Wenzhe Li,Jiandong Fan","doi":"10.1039/d6cp03410a","DOIUrl":"https://doi.org/10.1039/d6cp03410a","url":null,"abstract":"The mechanisms governing defect formation in perovskite single-crystal growth remain elusive due to the complex interplay of kinetic, thermal, and compositional factors, which vary across different growth methods and durations. Here, we develop an explainable machine learning framework using XGBoost to decode these mechanisms across three physically distinct growth scale. By integrating physically informed descriptors with SHAP and partial dependence analyses, we uncover a systematic evolution of dominant control factors: from nucleation-growth balance at short time scale, through thermo-structure regulation at intermediate time scale, to environmental stability at long time scale. Our results demonstrate that optimal growth conditions are not universal but shift with the dominant physical process, providing a method-agnostic, interpretable strategy for defect-minimized single-crystal growth. This study demonstrates an interpretable machine learning strategy for discovering growth mechanisms of different time scales and provides guidance for optimizing single crystal growth conditions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"45 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151972","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}