Pub Date : 2026-03-24DOI: 10.1021/acs.jpclett.6c00444
Yuqi Wu,Xiaodan Yan,Ting Meng,Jinlu He
Experimental studies have demonstrated that doping magnetic ions into halide perovskites offers a promising route to tailor electron spin dynamics and suppress nonradiative charge recombination, yet the underlying atomistic mechanism remains elusive. Using nonadiabatic molecular dynamics simulations, we demonstrate that Mn doping in CsPbBr3 enhances spin polarization without introducing midgap trap states compared to the pristine system. This spin polarization reduces nonadiabatic coupling between band-edge states while activating additional spin-orbit coupling (SOC)-mediated spin-flip channels within CBM↑/CBM↓ and VBM↑/VBM↓. These channels enable dynamic charge redistribution among spin-resolved orbitals, thereby prolonging carrier lifetimes. Our study reveals how band-edge SOC governs charge recombination and spin relaxation dynamics in halide perovskites, providing design principles for high-performance optoelectronic devices.
{"title":"Tuning Band-Edge Spin-Orbit Coupling to Prolong Carrier Lifetime in CsPbBr3 Perovskites.","authors":"Yuqi Wu,Xiaodan Yan,Ting Meng,Jinlu He","doi":"10.1021/acs.jpclett.6c00444","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00444","url":null,"abstract":"Experimental studies have demonstrated that doping magnetic ions into halide perovskites offers a promising route to tailor electron spin dynamics and suppress nonradiative charge recombination, yet the underlying atomistic mechanism remains elusive. Using nonadiabatic molecular dynamics simulations, we demonstrate that Mn doping in CsPbBr3 enhances spin polarization without introducing midgap trap states compared to the pristine system. This spin polarization reduces nonadiabatic coupling between band-edge states while activating additional spin-orbit coupling (SOC)-mediated spin-flip channels within CBM↑/CBM↓ and VBM↑/VBM↓. These channels enable dynamic charge redistribution among spin-resolved orbitals, thereby prolonging carrier lifetimes. Our study reveals how band-edge SOC governs charge recombination and spin relaxation dynamics in halide perovskites, providing design principles for high-performance optoelectronic devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"270 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502185","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 : 2026-03-23DOI: 10.1021/acs.jpclett.6c00555
Ahmad Ostovari Moghaddam,Seyedsaeed Mehrabi-Kalajahi,Seyed Amir Hossein Vasigh,Hassan Yousefi Bavili,Behrouz Shaabani,Xue Bai,Wei Qin,Alexei Vagov,Andrey S Vasenko,Fu-Quan Bai,Mikhail A Varfolomeev
Water electrolysis is a key technology for sustainable energy conversion and hydrogen generation. Recently, high-entropy oxides (HEOs) have emerged as promising materials because they allow tuning of structural, electronic, and catalytic properties in multifunctional systems. Here, we report the synthesis of a multicomponent La(FeCoCuTiNiMnMgSnZn)O3 perovskite, and its hybridization with reduced graphene oxide (rGO) to form a robust La(FeCoCuTiNiMnMgSnZn)O3-rGO nanocomposite. Structural characterization confirms the formation of a single-phase cubic perovskite structure with a uniform cation distribution and a slight lattice expansion compared with LaTiO3. In addition, HEO nanoparticles are homogeneously dispersed on the rGO sheets. High-resolution XPS analysis also reveals a defect-rich surface with mixed metal valence states, which interact with the conductive carbon network. Electrochemical measurements show that the La(FeCoCuTiNiMnMgSnZn)O3-rGO nanocomposite exhibits superior oxygen evolution reaction (OER) activity. It reaches a current density of 30 mA cm-2 at a lower overpotential and shows a Tafel slope of 81.9 mV dec-1. The catalyst also demonstrates good stability during 8 h of continuous operation. The enhanced performance is attributed to the combined effect of multiple metal elements in the high-entropy lattice, improved charge transport through the rGO network, and the presence of many active sites created by surface defects. These results show that combining HEOs with conductive carbon materials is a useful strategy for developing efficient and durable electrocatalysts for the OER.
水电解是可持续能源转化和制氢的关键技术。最近，高熵氧化物（HEOs）作为一种很有前途的材料出现，因为它们允许在多功能系统中调整结构、电子和催化性能。在这里，我们报道了一种多组分La(FeCoCuTiNiMnMgSnZn)O3钙钛矿的合成，并将其与还原氧化石墨烯（rGO）杂化，形成了一种坚固的La(FeCoCuTiNiMnMgSnZn)O3-rGO纳米复合材料。结构表征证实形成了一种阳离子分布均匀的单相立方钙钛矿结构，与LaTiO3相比有轻微的晶格膨胀。此外，HEO纳米颗粒均匀地分散在氧化石墨烯薄片上。高分辨率XPS分析还揭示了具有混合金属价态的富含缺陷的表面，这些缺陷与导电碳网络相互作用。电化学测试表明，La(FeCoCuTiNiMnMgSnZn)O3-rGO纳米复合材料具有优异的析氧反应（OER）活性。在较低的过电位下，电流密度达到30 mA cm-2，塔非尔斜率为81.9 mV / dec1。催化剂在连续运行8 h时也表现出良好的稳定性。这种性能的增强是由于高熵晶格中多种金属元素的综合作用，通过还原氧化石墨烯网络的电荷传输的改善，以及表面缺陷产生的许多活性位点的存在。这些结果表明，将氢氧根与导电碳材料结合是开发高效、耐用的OER电催化剂的有效策略。
{"title":"Synergistic Multimetal Effects in a High-Entropy Perovskite Oxide Anchored on Reduced Graphene Oxide for Accelerated Water Oxidation.","authors":"Ahmad Ostovari Moghaddam,Seyedsaeed Mehrabi-Kalajahi,Seyed Amir Hossein Vasigh,Hassan Yousefi Bavili,Behrouz Shaabani,Xue Bai,Wei Qin,Alexei Vagov,Andrey S Vasenko,Fu-Quan Bai,Mikhail A Varfolomeev","doi":"10.1021/acs.jpclett.6c00555","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00555","url":null,"abstract":"Water electrolysis is a key technology for sustainable energy conversion and hydrogen generation. Recently, high-entropy oxides (HEOs) have emerged as promising materials because they allow tuning of structural, electronic, and catalytic properties in multifunctional systems. Here, we report the synthesis of a multicomponent La(FeCoCuTiNiMnMgSnZn)O3 perovskite, and its hybridization with reduced graphene oxide (rGO) to form a robust La(FeCoCuTiNiMnMgSnZn)O3-rGO nanocomposite. Structural characterization confirms the formation of a single-phase cubic perovskite structure with a uniform cation distribution and a slight lattice expansion compared with LaTiO3. In addition, HEO nanoparticles are homogeneously dispersed on the rGO sheets. High-resolution XPS analysis also reveals a defect-rich surface with mixed metal valence states, which interact with the conductive carbon network. Electrochemical measurements show that the La(FeCoCuTiNiMnMgSnZn)O3-rGO nanocomposite exhibits superior oxygen evolution reaction (OER) activity. It reaches a current density of 30 mA cm-2 at a lower overpotential and shows a Tafel slope of 81.9 mV dec-1. The catalyst also demonstrates good stability during 8 h of continuous operation. The enhanced performance is attributed to the combined effect of multiple metal elements in the high-entropy lattice, improved charge transport through the rGO network, and the presence of many active sites created by surface defects. These results show that combining HEOs with conductive carbon materials is a useful strategy for developing efficient and durable electrocatalysts for the OER.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495051","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 : 2026-03-23DOI: 10.1021/acs.jpclett.6c00372
Jiaren Huang,Xiaodong Shen,Yongqiang Zhao,Weixing Chen,Tao Huang,Bingsuo Zou
In this work, BaCl2:Eu2+,S2- is employed as model system to investigate the formation and tunable evolution of localized excitonic magnetic polarons (LEMPs) in Eu-S codoped divalent metal halides, in which Eu-S bonding in BaCl2 with Eu2+ 5d-f hybridization markedly enhances the band edge emission, shifting from 401 to 412 nm with rising EuS content, and the absorption band edge shifts from 3.02 to 2.85 eV, with EMP character. Moreover, EuS doped in different hosts (Ba < Sr < Ca) leads to a progressive red shift of EMP emission from 406 nm to the near-infrared region. Under high-energy laser excitation, these compounds can exhibit pronounced nonlinear emission with ASE-like behavior (n > 1), demonstrating the LEMP-cooperative radiative processes. This study establishes rare-earth-sulfur codoped halides as a promising materials platform for tuning luminescence through coupled spin-lattice-exciton interactions.
{"title":"Localized Excitonic Magnetic Polarons and Their Role in the Luminescence of Rare-Earth-Sulfur Codoped Divalent Metal Halides.","authors":"Jiaren Huang,Xiaodong Shen,Yongqiang Zhao,Weixing Chen,Tao Huang,Bingsuo Zou","doi":"10.1021/acs.jpclett.6c00372","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00372","url":null,"abstract":"In this work, BaCl2:Eu2+,S2- is employed as model system to investigate the formation and tunable evolution of localized excitonic magnetic polarons (LEMPs) in Eu-S codoped divalent metal halides, in which Eu-S bonding in BaCl2 with Eu2+ 5d-f hybridization markedly enhances the band edge emission, shifting from 401 to 412 nm with rising EuS content, and the absorption band edge shifts from 3.02 to 2.85 eV, with EMP character. Moreover, EuS doped in different hosts (Ba < Sr < Ca) leads to a progressive red shift of EMP emission from 406 nm to the near-infrared region. Under high-energy laser excitation, these compounds can exhibit pronounced nonlinear emission with ASE-like behavior (n > 1), demonstrating the LEMP-cooperative radiative processes. This study establishes rare-earth-sulfur codoped halides as a promising materials platform for tuning luminescence through coupled spin-lattice-exciton interactions.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"31 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502189","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 : 2026-03-23DOI: 10.1021/acs.jpclett.6c00411
Yongjie Fan,RuiYa Xu,Wen Yang,Hongwei Xia,Yufang Liu
The image data obtained from solid-state, two-dimensional (2D) broadband photodetectors enable enhanced object identification owing to the wide range of information residing beyond human vision capabilities. However, the widespread use of these photodetector devices is limited by narrow photoresponse ranges and low response speeds. The obtained 2D InSbSe3 photodetector devices exhibit comprehensively excellent optoelectronic properties with a high on/off ratio of 105, a high photoresponsivity of 5.14 A/W, and an ultrashort photoresponse time of 6 ms under laser illumination at a wavelength of 520 nm with an applied bias voltage of 0.2 V. These metrics represent a greater performance than those obtained by most previously reported photodetector devices composed of other 2D ternary materials. Furthermore, the InSbSe3-based photodetector devices demonstrate a favorable broadband photoresponse, with good performance obtained at wavelengths ranging from ultraviolet (265 nm) to near-infrared (940 nm). Finally, the developed photodetector devices facilitated optical imaging conducted at wavelengths of 375, 520, and 785 nm. Accordingly, the proposed 2D InSbSe3 nanosheet materials exhibit a substantial potential for the development of low-power, high-sensitivity multispectral imaging systems useful in a wide range of applications such as machine vision, environmental monitoring, and medical diagnosis.
从固态、二维（2D）宽带光电探测器获得的图像数据，由于人类视觉能力之外的广泛信息，能够增强物体识别。然而，这些光电探测器器件的广泛使用受到光响应范围窄和响应速度低的限制。所制得的二维InSbSe3光电探测器器件在520 nm波长、0.2 V偏置电压的激光照射下，具有105的高开/关比、5.14 a /W的高光响应率和6 ms的超短光响应时间等综合优异的光电性能。这些指标比以前报道的大多数由其他二维三元材料组成的光电探测器器件获得的性能更好。此外，基于insbse3的光电探测器器件表现出良好的宽带光响应，在紫外（265 nm）到近红外（940 nm）波长范围内都有良好的性能。最后，所开发的光电探测器装置有助于在375、520和785 nm波长下进行光学成像。因此，所提出的二维InSbSe3纳米片材料在开发低功耗、高灵敏度多光谱成像系统方面具有巨大潜力，可用于机器视觉、环境监测和医疗诊断等广泛应用。
{"title":"Atomically Thin InSbSe3 Layers for Multispectral Optical Imaging with Fast Photoresponse and Broadband Photodetection.","authors":"Yongjie Fan,RuiYa Xu,Wen Yang,Hongwei Xia,Yufang Liu","doi":"10.1021/acs.jpclett.6c00411","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00411","url":null,"abstract":"The image data obtained from solid-state, two-dimensional (2D) broadband photodetectors enable enhanced object identification owing to the wide range of information residing beyond human vision capabilities. However, the widespread use of these photodetector devices is limited by narrow photoresponse ranges and low response speeds. The obtained 2D InSbSe3 photodetector devices exhibit comprehensively excellent optoelectronic properties with a high on/off ratio of 105, a high photoresponsivity of 5.14 A/W, and an ultrashort photoresponse time of 6 ms under laser illumination at a wavelength of 520 nm with an applied bias voltage of 0.2 V. These metrics represent a greater performance than those obtained by most previously reported photodetector devices composed of other 2D ternary materials. Furthermore, the InSbSe3-based photodetector devices demonstrate a favorable broadband photoresponse, with good performance obtained at wavelengths ranging from ultraviolet (265 nm) to near-infrared (940 nm). Finally, the developed photodetector devices facilitated optical imaging conducted at wavelengths of 375, 520, and 785 nm. Accordingly, the proposed 2D InSbSe3 nanosheet materials exhibit a substantial potential for the development of low-power, high-sensitivity multispectral imaging systems useful in a wide range of applications such as machine vision, environmental monitoring, and medical diagnosis.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"7 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495053","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 : 2026-03-23DOI: 10.1021/acs.jpclett.6c00524
Mohamed Sabba, Christian Bengs, Urvashi D Heramun, Malcolm H Levitt
A modification of the widely used spin-lock-induced crossing (SLIC) procedure is proposed for the solution nuclear magnetic resonance (NMR) of strongly coupled nuclear spin systems, including singlet NMR and parahydrogen-enhanced hyperpolarized NMR experiments. The compensated-SLIC (cSLIC) scheme uses a repetitive sequence where the repeated element employs two different radio-frequency field amplitudes. Effective compensation for deviations in the radio-frequency field amplitude is achieved without increasing the overall duration of the SLIC sequence. The advantageous properties of cSLIC are demonstrated by numerical simulations and representative experiments.
{"title":"Error Compensation without a Time Penalty: Robust Spin-Lock-Induced Crossing in Solution NMR.","authors":"Mohamed Sabba, Christian Bengs, Urvashi D Heramun, Malcolm H Levitt","doi":"10.1021/acs.jpclett.6c00524","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00524","url":null,"abstract":"<p><p>A modification of the widely used spin-lock-induced crossing (SLIC) procedure is proposed for the solution nuclear magnetic resonance (NMR) of strongly coupled nuclear spin systems, including singlet NMR and parahydrogen-enhanced hyperpolarized NMR experiments. The compensated-SLIC (cSLIC) scheme uses a repetitive sequence where the repeated element employs two different radio-frequency field amplitudes. Effective compensation for deviations in the radio-frequency field amplitude is achieved without increasing the overall duration of the SLIC sequence. The advantageous properties of cSLIC are demonstrated by numerical simulations and representative experiments.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502595","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 : 2026-03-23DOI: 10.1021/acs.jpclett.6c00410
Ulrich Leo,Maximilian A Gruber,Nina A Henke,Veronika Reisner,Sirri B Kalkan,Michael F Lichtenegger,Bert Nickel,Alexander S Urban
Lead halide perovskite nanocrystals (PNCs) exhibit outstanding optical and electronic properties for next-generation optoelectronics; however, their instability under ambient conditions severely hinders their practical implementation. Here, we demonstrate a versatile ligand cross-linking approach via electron-beam irradiation that effectively enhances nanocrystal stability without compromising their exceptional optical properties. Electron-beam exposure induces cross-linking reactions within the native oleylamine and oleic acid ligand shell, forming a robust, interconnected organic network that substantially increases hydrophobicity, long-term ambient stability, and resistance to various solvents. Unlike polymer or micelle encapsulation strategies, our cross-linking method preserves the structural integrity of the PNC layer and its optical properties without introducing additional layers or barriers that could impede charge transport. We further exploit this technique to create unprecedented heterostructures, achieving dual-emission spectra without ion exchange. Additionally, we present a novel method for producing mechanically stable, freestanding PNC films, which significantly simplifies device fabrication. These findings open up new avenues for integrating highly stable perovskite nanocrystal layers into commercial-scale photovoltaic and optoelectronic devices.
{"title":"Electron-Beam Cross-Linked Ligands Enable Highly Stable and Freestanding Perovskite Nanocrystal Films.","authors":"Ulrich Leo,Maximilian A Gruber,Nina A Henke,Veronika Reisner,Sirri B Kalkan,Michael F Lichtenegger,Bert Nickel,Alexander S Urban","doi":"10.1021/acs.jpclett.6c00410","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00410","url":null,"abstract":"Lead halide perovskite nanocrystals (PNCs) exhibit outstanding optical and electronic properties for next-generation optoelectronics; however, their instability under ambient conditions severely hinders their practical implementation. Here, we demonstrate a versatile ligand cross-linking approach via electron-beam irradiation that effectively enhances nanocrystal stability without compromising their exceptional optical properties. Electron-beam exposure induces cross-linking reactions within the native oleylamine and oleic acid ligand shell, forming a robust, interconnected organic network that substantially increases hydrophobicity, long-term ambient stability, and resistance to various solvents. Unlike polymer or micelle encapsulation strategies, our cross-linking method preserves the structural integrity of the PNC layer and its optical properties without introducing additional layers or barriers that could impede charge transport. We further exploit this technique to create unprecedented heterostructures, achieving dual-emission spectra without ion exchange. Additionally, we present a novel method for producing mechanically stable, freestanding PNC films, which significantly simplifies device fabrication. These findings open up new avenues for integrating highly stable perovskite nanocrystal layers into commercial-scale photovoltaic and optoelectronic devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"118 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495052","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.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。
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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}
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