Pub Date : 2026-03-22DOI: 10.1021/acs.jpclett.6c00621
Tatsuki Hosoda,Asuka Fujii
The hemibond, a nonclassical covalent interaction arising from charge-resonance between a radical and a neutral molecule, represents a distinctive bonding motif in open-shell systems. Its role has been widely discussed in radical reactions, radiation chemistry, and related biochemical processes. While hemibonds involving water molecules have garnered considerable interest, it remains unclear whether these interactions can persist under bulk solvation conditions. Here, we investigate hemibond formation in gas-phase [H2O-X]+ clusters and examine the structural evolution upon microhydration. Infrared photodissociation spectroscopy of [H2O-X]+-(H2O)n (X = O2 and CS2; n = 0-2) reveals that the hemibonded structure of [H2O-X]+ persists during microhydration. These results elucidate the interplay between charge-resonance and charge-(induced) dipole interactions that govern hemibond stability and suggest that certain molecules may retain the ability to form stable hemibonds with water even in aqueous environments.
半键是由自由基和中性分子之间的电荷共振引起的非经典共价相互作用，是开壳体系中独特的键基序。它在自由基反应、辐射化学和相关生化过程中的作用已被广泛讨论。虽然涉及水分子的半键引起了相当大的兴趣，但这些相互作用是否能在体溶剂化条件下持续存在仍不清楚。在这里，我们研究了气相[H2O-X]+团簇中的半键形成，并研究了微水化作用下的结构演变。[H2O-X]+-(H2O)n （X = O2和CS2； n = 0-2）的红外光解光谱显示[H2O-X]+的半键结构在微水化过程中持续存在。这些结果阐明了控制半键稳定性的电荷共振和电荷（诱导）偶极相互作用之间的相互作用，并表明某些分子即使在水环境中也可能保留与水形成稳定半键的能力。
{"title":"Microhydration Effects on Hemibonds in [H2O-X]+-(H2O)n (X = O2 and CS2; n = 0-2): Infrared Spectroscopic Characterization toward Understanding Charge-Resonance Interactions in Aqueous Environments.","authors":"Tatsuki Hosoda,Asuka Fujii","doi":"10.1021/acs.jpclett.6c00621","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00621","url":null,"abstract":"The hemibond, a nonclassical covalent interaction arising from charge-resonance between a radical and a neutral molecule, represents a distinctive bonding motif in open-shell systems. Its role has been widely discussed in radical reactions, radiation chemistry, and related biochemical processes. While hemibonds involving water molecules have garnered considerable interest, it remains unclear whether these interactions can persist under bulk solvation conditions. Here, we investigate hemibond formation in gas-phase [H2O-X]+ clusters and examine the structural evolution upon microhydration. Infrared photodissociation spectroscopy of [H2O-X]+-(H2O)n (X = O2 and CS2; n = 0-2) reveals that the hemibonded structure of [H2O-X]+ persists during microhydration. These results elucidate the interplay between charge-resonance and charge-(induced) dipole interactions that govern hemibond stability and suggest that certain molecules may retain the ability to form stable hemibonds with water even in aqueous environments.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"49 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495085","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}
Pub Date : 2026-03-22DOI: 10.1021/acs.jpclett.5c03904
Wei Qiu,Baidu Zhang,Linghui He,Yong Ni
Compression strain-induced dislocation and ripplocation structures are crucial for the unique properties of van der Waals layered materials. While previous studies have primarily focused on the dislocation–ripplocation transformation under thermodynamic equilibrium, the metastability of this transformation remains underexplored. This work theoretically reports the existence of a metastable region for the dislocation–ripplocation structural transformation in bilayer graphene under uniaxial compression. Using nudged elastic band calculations, we identify a nonzero energy barrier between the two structures, indicating metastability within a specific strain range εi ≤ ε0 ≤ εe. Outside this range, only one local minimum exists: dislocation at ε0 < εi and ripplocation at ε0 > εe. Furthermore, we investigate the size dependence of the two critical strains that bound the metastable region, finding that the difference between them, εe – εi, increases with the sample length. This structural transformation profoundly affects the material’s physical properties, such as tribological behavior. These findings reveal the metastable nature of dislocation–ripplocation transformation and offer valuable insights into strain-engineered morphologies of layered materials, with implications for the mechanical behavior and design of nanodevices.
{"title":"Metastability and Size Effect during Transformation from Dislocation to Ripplocation in Bilayer Graphene","authors":"Wei Qiu,Baidu Zhang,Linghui He,Yong Ni","doi":"10.1021/acs.jpclett.5c03904","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03904","url":null,"abstract":"Compression strain-induced dislocation and ripplocation structures are crucial for the unique properties of van der Waals layered materials. While previous studies have primarily focused on the dislocation–ripplocation transformation under thermodynamic equilibrium, the metastability of this transformation remains underexplored. This work theoretically reports the existence of a metastable region for the dislocation–ripplocation structural transformation in bilayer graphene under uniaxial compression. Using nudged elastic band calculations, we identify a nonzero energy barrier between the two structures, indicating metastability within a specific strain range εi ≤ ε0 ≤ εe. Outside this range, only one local minimum exists: dislocation at ε0 < εi and ripplocation at ε0 > εe. Furthermore, we investigate the size dependence of the two critical strains that bound the metastable region, finding that the difference between them, εe – εi, increases with the sample length. This structural transformation profoundly affects the material’s physical properties, such as tribological behavior. These findings reveal the metastable nature of dislocation–ripplocation transformation and offer valuable insights into strain-engineered morphologies of layered materials, with implications for the mechanical behavior and design of nanodevices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"82 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147493141","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}
Pub Date : 2026-03-20DOI: 10.1021/acs.jpclett.6c00493
Thanh T Lai,Charles L Brooks Iii
Molecular simulation in the grand canonical ensemble is widely used to study a diverse range of systems and processes, such as water networks in biological macromolecules, drug binding, and the adsorption of molecules at an interface. Here, we develop grand canonical multisite lambda dynamics (GC-MSλD) to sample fluctuations in molecule number by coupling the molecules of interest to a dynamic λ variable. The chemical potential, set as a λ-dependent energetic bias, is used to control the number of molecules. We anticipate that GC-MSλD may equilibrate faster and with less computational overhead than some GCMC/MD algorithms. We demonstrate the use of the GC-MSλD framework to control the number of molecules in a box of TIP3P water. Next, we apply the methodology to sample crystallographic water occupancies in a protein cavity and to compute protein-ligand binding free energies involving water displacement.
大正则系综中的分子模拟被广泛用于研究各种系统和过程，如生物大分子中的水网络、药物结合和分子在界面上的吸附。在这里，我们通过将感兴趣的分子与动态λ变量耦合，开发了大规范多位点λ动力学（gc - ms - λ d）来采样分子数的波动。化学势，设置为λ依赖的能量偏差，用来控制分子的数量。我们预计gc - ms - λ d可能比一些GCMC/MD算法更快，计算开销更少。我们演示了使用gc - ms - λ d框架来控制一盒TIP3P水中的分子数量。接下来，我们将该方法应用于蛋白质空腔中晶体水占用的样品，并计算涉及水位移的蛋白质-配体结合自由能。
{"title":"Sampling the Grand Canonical Ensemble with Multisite λ Dynamics.","authors":"Thanh T Lai,Charles L Brooks Iii","doi":"10.1021/acs.jpclett.6c00493","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00493","url":null,"abstract":"Molecular simulation in the grand canonical ensemble is widely used to study a diverse range of systems and processes, such as water networks in biological macromolecules, drug binding, and the adsorption of molecules at an interface. Here, we develop grand canonical multisite lambda dynamics (GC-MSλD) to sample fluctuations in molecule number by coupling the molecules of interest to a dynamic λ variable. The chemical potential, set as a λ-dependent energetic bias, is used to control the number of molecules. We anticipate that GC-MSλD may equilibrate faster and with less computational overhead than some GCMC/MD algorithms. We demonstrate the use of the GC-MSλD framework to control the number of molecules in a box of TIP3P water. Next, we apply the methodology to sample crystallographic water occupancies in a protein cavity and to compute protein-ligand binding free energies involving water displacement.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"13 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490187","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}
Pub Date : 2026-03-20DOI: 10.1021/acs.jpclett.6c00287
Shih-Yong Chen,Chin-Hong Goh,Mayumi Egashira,Chun-Yu Chen,Jhih-Min Lin,Chien-Lung Wang
Deformability is a key pathway to structural complexity in self-assembled systems. Although numerous molecular systems have been engineered to form Frank-Kasper (FK) phases, they typically rely on size- or shape-based asymmetries rather than new structural degrees of freedom. By incorporating chain-length asymmetry into dendritic amphiphiles, this study endows supramolecular micelles in the soft FK σ phase with a controllable deformability. The asymmetric dendrons (ADs) form anisotropic σ phases with domain-dependent diffraction patterns caused by micelle deformation, as verified by the anisotropic Debye-Waller simulations. Over time, these anisotropic micelles reorganize along specific planes, triggering a σ-to-lamellar transition. Incorporating hydrophobic guest molecules compensates for the chain-length asymmetry, switching off deformability and restoring isotropic packing. Thus, deformability emerges as a tunable parameter governing lattice symmetry and phase evolution, offering a design principle for scalable and hierarchically complex assemblies.
{"title":"On and Off Deformability of Supramolecular Micelles in the Soft Frank-Kasper σ Phase.","authors":"Shih-Yong Chen,Chin-Hong Goh,Mayumi Egashira,Chun-Yu Chen,Jhih-Min Lin,Chien-Lung Wang","doi":"10.1021/acs.jpclett.6c00287","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00287","url":null,"abstract":"Deformability is a key pathway to structural complexity in self-assembled systems. Although numerous molecular systems have been engineered to form Frank-Kasper (FK) phases, they typically rely on size- or shape-based asymmetries rather than new structural degrees of freedom. By incorporating chain-length asymmetry into dendritic amphiphiles, this study endows supramolecular micelles in the soft FK σ phase with a controllable deformability. The asymmetric dendrons (ADs) form anisotropic σ phases with domain-dependent diffraction patterns caused by micelle deformation, as verified by the anisotropic Debye-Waller simulations. Over time, these anisotropic micelles reorganize along specific planes, triggering a σ-to-lamellar transition. Incorporating hydrophobic guest molecules compensates for the chain-length asymmetry, switching off deformability and restoring isotropic packing. Thus, deformability emerges as a tunable parameter governing lattice symmetry and phase evolution, offering a design principle for scalable and hierarchically complex assemblies.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"2 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147483565","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}
The anisotropy of surface structures in metal oxide-based semiconductor photocatalysts plays a critical role in governing photoactivated gas sensing properties. However, the surface reaction mechanism of the photochemical behavior remains poorly understood at the atomic scale. In this study, using CuO nanomaterials with various morphologies as a model system, including nanoparticles (NPs), nanorods (NRs), and nanosheets (NSs), we identified their surface atomic structures through aberration-corrected scanning transmission electron microscopy and first-principles calculation. We revealed the distinct surface reconstruction behaviors of the low Miller index surfaces. Photochemical sensing measurements showed that CuO NRs and CuO NSs, which predominantly expose oxygen-terminated (100) and copper-terminated (001) surfaces, respectively, exhibited optimized photoresponses toward H2S and CH3SH molecules. The concurrent adsorption of target molecules was revealed as the rate-determining step of the photocatalytic conversion. This work provides fundamental avenues for the predictive design and manipulation of surface reconstructions in metal oxides for a broad range of catalytic and sensing applications.
{"title":"Structure-Function Relationship of Surface Reconstruction in Cupric Oxide for Photochemical Sensing Properties.","authors":"Wandong Xing,Feifei Huang,Xiaoyan Li,Fei Zhao,Mingyue Wang,Shilan Zhang,Xiaocong Liang,Sikang Xue,Can Yang,Zhiyang Yu","doi":"10.1021/acs.jpclett.6c00467","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00467","url":null,"abstract":"The anisotropy of surface structures in metal oxide-based semiconductor photocatalysts plays a critical role in governing photoactivated gas sensing properties. However, the surface reaction mechanism of the photochemical behavior remains poorly understood at the atomic scale. In this study, using CuO nanomaterials with various morphologies as a model system, including nanoparticles (NPs), nanorods (NRs), and nanosheets (NSs), we identified their surface atomic structures through aberration-corrected scanning transmission electron microscopy and first-principles calculation. We revealed the distinct surface reconstruction behaviors of the low Miller index surfaces. Photochemical sensing measurements showed that CuO NRs and CuO NSs, which predominantly expose oxygen-terminated (100) and copper-terminated (001) surfaces, respectively, exhibited optimized photoresponses toward H2S and CH3SH molecules. The concurrent adsorption of target molecules was revealed as the rate-determining step of the photocatalytic conversion. This work provides fundamental avenues for the predictive design and manipulation of surface reconstructions in metal oxides for a broad range of catalytic and sensing applications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"85 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490189","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}
Pub Date : 2026-03-20DOI: 10.1021/acs.jpclett.6c00128
Blair A Welsh,Judit Zádor,Sven Herbers,Edwin L Sibert,Timothy S Zwier
2,6-Dimethylphenol has three internal rotors: two methyl rotors taking up positions ortho to the phenol-OH group and the OH rotor itself. We recorded the broadband microwave spectrum of 2,6-dimethylphenol over the 7.5-17.5 GHz range under jet-cooled conditions in the gas phase. In contrast to the tunneling doublets observed in phenol, a-type rotational transitions in 2,6-dimethylphenol appear as equally spaced triplets, with the two outer components split by ± 48.54 MHz relative to the central line. We fit the spectrum using a model in which OH tunneling either occurs or is quenched, depending on whether the two methyl rotors are in AA/EE states (tunneling present) or AE/EA states (tunneling quenched). Tunneling of the OH group is quenched in the AE/EA methyl rotor states due to OH/CH3 coupling that modulates the methyl rotor barrier height by almost a factor of 2, depending on the OH orientation relative to the methyl group. This, in turn, changes the energy of the AE and EA methyl rotor states, producing an effective asymmetry in the OH tunneling coordinate that is significantly greater than the tunneling splitting. This localizes the OH torsional wave functions in one or the other of the two wells. By contrast, the a-type rotational transitions in the AA and EE methyl rotor states possess a tunneling splitting similar to that observed in phenol. We compare and contrast the case of state-dependent quenching of tunneling encountered here to the reduction in tunneling splitting that can occur in asymmetric vibrational states.
{"title":"Methyl Rotor State-Dependent Quenching of OH Tunneling in 2,6-Dimethylphenol.","authors":"Blair A Welsh,Judit Zádor,Sven Herbers,Edwin L Sibert,Timothy S Zwier","doi":"10.1021/acs.jpclett.6c00128","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00128","url":null,"abstract":"2,6-Dimethylphenol has three internal rotors: two methyl rotors taking up positions ortho to the phenol-OH group and the OH rotor itself. We recorded the broadband microwave spectrum of 2,6-dimethylphenol over the 7.5-17.5 GHz range under jet-cooled conditions in the gas phase. In contrast to the tunneling doublets observed in phenol, a-type rotational transitions in 2,6-dimethylphenol appear as equally spaced triplets, with the two outer components split by ± 48.54 MHz relative to the central line. We fit the spectrum using a model in which OH tunneling either occurs or is quenched, depending on whether the two methyl rotors are in AA/EE states (tunneling present) or AE/EA states (tunneling quenched). Tunneling of the OH group is quenched in the AE/EA methyl rotor states due to OH/CH3 coupling that modulates the methyl rotor barrier height by almost a factor of 2, depending on the OH orientation relative to the methyl group. This, in turn, changes the energy of the AE and EA methyl rotor states, producing an effective asymmetry in the OH tunneling coordinate that is significantly greater than the tunneling splitting. This localizes the OH torsional wave functions in one or the other of the two wells. By contrast, the a-type rotational transitions in the AA and EE methyl rotor states possess a tunneling splitting similar to that observed in phenol. We compare and contrast the case of state-dependent quenching of tunneling encountered here to the reduction in tunneling splitting that can occur in asymmetric vibrational states.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"115 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490186","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}
High-entropy metal oxides represent an emerging and conceptually distinct platform for developing innovative visible-light-active photocatalysts for solar-driven water splitting. Here, we report the rational synthesis of a gallate-based high-entropy spinel oxide photocatalyst, Fe0.3Co0.3Ni0.3Cu0.3Zn0.3Ga1.5O4 (Ga1.5-HES), for a visible-light-driven oxygen-evolution reaction (OER). Through deliberately reducing the ratio of Ga to transition metals below the conventional stoichiometry of spinel gallates, the OER-active Fe/Co/Ni elements are driven to occupy both tetrahedral and octahedral sublattices of the spinel lattice, resulting in the mixed valence states that effectively optimize the catalytically active centers for oxygen evolution. The resulting Ga1.5-HES exhibits a tailored electronic structure with a narrow bandgap of ∼2.15 eV and band-edge positions suitable for water oxidation. Under visible-light irradiation and without any cocatalyst, Ga1.5-HES achieves efficient oxygen evolution with an apparent quantum yield (AQY) of ∼1.7% at 450 nm, and further enables stoichiometric overall water splitting when integrated into a mediator-assisted indirect Z-scheme.
{"title":"High-Entropy Spinel Gallate Photocatalyst for Visible-Light-Driven Water Oxidation.","authors":"Meiyun Li,Lejuan Cai,Hao Ling,Zheheng Huang,Lisha Lu,Renjie Li,Yuanfang Feng,Muhua Sun,Xuedong Bai,Wenlong Wang","doi":"10.1021/acs.jpclett.6c00479","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00479","url":null,"abstract":"High-entropy metal oxides represent an emerging and conceptually distinct platform for developing innovative visible-light-active photocatalysts for solar-driven water splitting. Here, we report the rational synthesis of a gallate-based high-entropy spinel oxide photocatalyst, Fe0.3Co0.3Ni0.3Cu0.3Zn0.3Ga1.5O4 (Ga1.5-HES), for a visible-light-driven oxygen-evolution reaction (OER). Through deliberately reducing the ratio of Ga to transition metals below the conventional stoichiometry of spinel gallates, the OER-active Fe/Co/Ni elements are driven to occupy both tetrahedral and octahedral sublattices of the spinel lattice, resulting in the mixed valence states that effectively optimize the catalytically active centers for oxygen evolution. The resulting Ga1.5-HES exhibits a tailored electronic structure with a narrow bandgap of ∼2.15 eV and band-edge positions suitable for water oxidation. Under visible-light irradiation and without any cocatalyst, Ga1.5-HES achieves efficient oxygen evolution with an apparent quantum yield (AQY) of ∼1.7% at 450 nm, and further enables stoichiometric overall water splitting when integrated into a mediator-assisted indirect Z-scheme.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"31 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490190","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}
The buried interface between the perovskite and the tin oxide (SnO2) electron transport layer critically governs the efficiency and stability of perovskite solar cells (PSCs). Herein, we engineer a robust buried interface by constructing a dipolar molecular bridge using a multifunctional zwitterion, 4-(1,3,5-triaza-7-phosphaadamantan-1-ium-1-yl)butane-1-sulfonate (PTABS). The sulfonate group (─SO3-) of PTABS chemisorbs onto the SnO2 surface via stable Sn─O─S bonds, effectively passivating oxygen vacancies. Concurrently, the P and N atoms on the cationic side coordinate with undercoordinated Pb2+ in the perovskite, enabling bilateral interface passivation. Moreover, the superior hydrophilicity of PTABS improves the wettability of the SnO2 substrate, guiding the growth of a perovskite film with larger grains, reduced defects, and enhanced coverage. Crucially, the substantial intrinsic dipole moment of PTABS (computed to be 31.61 D) induces a strong interfacial dipole layer. This layer downshifts the work function of SnO2, promotes favorable band bending, and optimizes the energy-level alignment at the interface. Consequently, electron extraction and transport are significantly boosted, while hole back-transfer is effectively suppressed. As a result, PTABS-modified PSCs achieve an increased power conversion efficiency (PCE) of 24.13% compared to 22.37% for the control, along with markedly improved operational stability.
{"title":"Dipole Molecular Bridge Engineering Enables Defect Suppression and Charge Transport Enhancement at the Buried Interface of Perovskite Solar Cells.","authors":"Zhouwenjing Huang,Huaijing Li,Jiajun Zhu,Bing Yang,Yuyan Gu,Erdong Zhang,Bo Cai,Junmin Xia,Kun Cao,Shufen Chen","doi":"10.1021/acs.jpclett.6c00286","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00286","url":null,"abstract":"The buried interface between the perovskite and the tin oxide (SnO2) electron transport layer critically governs the efficiency and stability of perovskite solar cells (PSCs). Herein, we engineer a robust buried interface by constructing a dipolar molecular bridge using a multifunctional zwitterion, 4-(1,3,5-triaza-7-phosphaadamantan-1-ium-1-yl)butane-1-sulfonate (PTABS). The sulfonate group (─SO3-) of PTABS chemisorbs onto the SnO2 surface via stable Sn─O─S bonds, effectively passivating oxygen vacancies. Concurrently, the P and N atoms on the cationic side coordinate with undercoordinated Pb2+ in the perovskite, enabling bilateral interface passivation. Moreover, the superior hydrophilicity of PTABS improves the wettability of the SnO2 substrate, guiding the growth of a perovskite film with larger grains, reduced defects, and enhanced coverage. Crucially, the substantial intrinsic dipole moment of PTABS (computed to be 31.61 D) induces a strong interfacial dipole layer. This layer downshifts the work function of SnO2, promotes favorable band bending, and optimizes the energy-level alignment at the interface. Consequently, electron extraction and transport are significantly boosted, while hole back-transfer is effectively suppressed. As a result, PTABS-modified PSCs achieve an increased power conversion efficiency (PCE) of 24.13% compared to 22.37% for the control, along with markedly improved operational stability.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"49 3 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147483564","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}
Pub Date : 2026-03-20DOI: 10.1021/acs.jpclett.6c00224
Xing Liu,Bowen Wang,Jiacheng Gong,Xuan Chen,Yongqing Cai
Metal halide perovskites have high compositional tunability, but halide mixing is often accompanied by phase segregation and instability in lead-free Sn-based systems. Here, we investigate the thermodynamics of Br/I alloying in CsSn(BrxI1-x)3 by combining density functional theory calculations with partition functions over all symmetry-inequivalent configurations of the cubic, tetragonal, and orthorhombic phases. We find that the orthorhombic phase exhibits the lowest mixing free-energy curve and is closest to the thermodynamic miscibility boundary, whereas the cubic phase remains the least favorable for Br/I mixing. At 300 K, the free-energy difference ΔFcub-orth = Fcub - Forth is positive over the entire composition range ((1.27-3.42)kBT), indicating a robust thermodynamic preference for the orthorhombic phase. The enhanced stability of the low-symmetry phase originates from more effective local structural relaxation. Our results further reveal a link between local octahedral distortions and thermodynamic stability, providing theoretical guidance for the compositional design of lead-free Sn-based mixed-halide perovskites.
{"title":"Configurational Entropy and Phase Stability in Lead-Free Mixed-Halide CsSn(BrxI1-x)3.","authors":"Xing Liu,Bowen Wang,Jiacheng Gong,Xuan Chen,Yongqing Cai","doi":"10.1021/acs.jpclett.6c00224","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00224","url":null,"abstract":"Metal halide perovskites have high compositional tunability, but halide mixing is often accompanied by phase segregation and instability in lead-free Sn-based systems. Here, we investigate the thermodynamics of Br/I alloying in CsSn(BrxI1-x)3 by combining density functional theory calculations with partition functions over all symmetry-inequivalent configurations of the cubic, tetragonal, and orthorhombic phases. We find that the orthorhombic phase exhibits the lowest mixing free-energy curve and is closest to the thermodynamic miscibility boundary, whereas the cubic phase remains the least favorable for Br/I mixing. At 300 K, the free-energy difference ΔFcub-orth = Fcub - Forth is positive over the entire composition range ((1.27-3.42)kBT), indicating a robust thermodynamic preference for the orthorhombic phase. The enhanced stability of the low-symmetry phase originates from more effective local structural relaxation. Our results further reveal a link between local octahedral distortions and thermodynamic stability, providing theoretical guidance for the compositional design of lead-free Sn-based mixed-halide perovskites.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"13 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490188","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}
Pub Date : 2026-03-20DOI: 10.1021/acs.jpclett.6c00584
Ze-Han Ma,Ming-Jia Yu,Shi-Lu Chen
Iron-sulfur ([FeS]) clusters often work as unidirectional electron-transfer conduits in metalloenzymes. Herein, we demonstrate that the [2Fe-2S]Rieske cluster in terephthalate 1,2-dioxygenase (TPADO) functions as a dynamic electron reservoir capable of bidirectional electron transfer during catalysis. Using density functional theory, we reveal that the TPADO reaction is driven by a previously unrecognized Rieske-assisted HO-FeIII═O•- species, rather than the canonical high-valent iron(V)-oxo. The Rieske cluster actively donates and retrieves electrons during O-O bond cleavage and substrate oxidation. Productive cis-dihydroxylation proceeds via stepwise oxo-initiated radical pathways, while Fe-OOH and epoxide-based mechanisms are ruled out by prohibitive barriers. These findings highlight the mechanistic role of Rieske clusters in oxygen activation, expanding the conceptual framework of both [FeS]-dependent and Fe-dependent catalysis.
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