Pub Date : 2026-10-21DOI: 10.1021/acs.jpclett.6c02695
Soham Chowdhury,Bijesh K. Malla,Thalappil Pradeep
We report the hydrolytic cleavage of C–O bonds in aliphatic ethers at cryogenic water ice surfaces under ultrahigh vacuum conditions. Ethers are conventionally resistant to hydrolysis, requiring strong Brønsted acids and elevated temperatures for C–O bond activation; their reactivity toward neutral water ice at temperatures as low as 10–50 K is therefore unexpected. Using Cs+ reactive ion scattering and low-energy sputtering in combination with isotopic labeling (H2O vs D2O), we demonstrate that dimethyl ether (DME), tert-butyl methyl ether (tBuOMe), and diethyl ether (DEE) undergo hydrolysis to form the corresponding deuterated alcohols upon contact with amorphous and crystalline D2O ice between 10 and 150 K. Isotopic incorporation establishes D2O ice as the source of the incorporated hydrogen. CH3OD was formed even at 10 K in codeposited DME-D2O films and it persisted on crystalline ice, while tBuOMe exhibited distinct product selectivity through the appearance of a tert-butyl carbocationic fragment in low-energy sputtering. These observations reveal an unexpected chemical reactivity of cryogenic water ice toward aliphatic ethers and establish ether hydrolysis as a previously unexplored low-temperature surface reaction.
我们报道了在超高真空条件下低温水冰表面脂肪醚中C-O键的水解裂解。醚通常不耐水解，需要强Brønsted酸和高温才能激活C-O键；因此，它们在低至10-50 K的温度下对中性水冰的反应性是出乎意料的。利用Cs+反应离子散射和低能溅射结合同位素标记（H2O vs D2O），我们证明了二甲醚（DME），叔丁基甲基醚（tBuOMe）和二乙醚（DEE）在10至150 K之间与非晶和结晶D2O冰接触时发生水解形成相应的氘化醇。同位素掺入确定了D2O冰是掺入氢的来源。在共沉积的DME-D2O薄膜中，CH3OD即使在10 K时也能形成，并在结晶冰上持续存在，而在低能溅射中，通过叔丁基碳阳离子碎片的出现，buome表现出明显的产物选择性。这些观察结果揭示了低温水冰对脂肪族醚的意想不到的化学反应性，并确立了醚水解是一个以前未被探索的低温表面反应。
{"title":"Spontaneous Ether Hydrolysis on Cryogenic Water Ice Surfaces","authors":"Soham Chowdhury,Bijesh K. Malla,Thalappil Pradeep","doi":"10.1021/acs.jpclett.6c02695","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02695","url":null,"abstract":"We report the hydrolytic cleavage of C–O bonds in aliphatic ethers at cryogenic water ice surfaces under ultrahigh vacuum conditions. Ethers are conventionally resistant to hydrolysis, requiring strong Brønsted acids and elevated temperatures for C–O bond activation; their reactivity toward neutral water ice at temperatures as low as 10–50 K is therefore unexpected. Using Cs+ reactive ion scattering and low-energy sputtering in combination with isotopic labeling (H2O vs D2O), we demonstrate that dimethyl ether (DME), tert-butyl methyl ether (tBuOMe), and diethyl ether (DEE) undergo hydrolysis to form the corresponding deuterated alcohols upon contact with amorphous and crystalline D2O ice between 10 and 150 K. Isotopic incorporation establishes D2O ice as the source of the incorporated hydrogen. CH3OD was formed even at 10 K in codeposited DME-D2O films and it persisted on crystalline ice, while tBuOMe exhibited distinct product selectivity through the appearance of a tert-butyl carbocationic fragment in low-energy sputtering. These observations reveal an unexpected chemical reactivity of cryogenic water ice toward aliphatic ethers and establish ether hydrolysis as a previously unexplored low-temperature surface reaction.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"13 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221724","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}
Bis(trifluoromethyl) sulfide (CF3SCF3) is a candidate insulating gas whose atmospheric persistence is poorly constrained: the structure–activity relationship cannot be reliably extrapolated to this perfluorinated species, and the only available theoretical estimate has not yet been tested against experiment. We measured the rate coefficient of its dominant atmospheric loss, reaction with OH, by pulsed laser photolysis–laser-induced fluorescence over 272–328 K at 50 Torr. The reaction is slow and nearly temperature independent, with k1(298 K) = (2.15 ± 0.34) × 10–15 cm3 molecule–1 s–1 and a slight positive trend (apparent Ea = (0.30 ± 0.14) kcal mol–1). No O2 dependence was detectable at 50 Torr. The measured k1 exceeds the theoretical value by approximately an order of magnitude, implying an OH-initiated lifetime of ∼14.7 years and a 100-year GWP of ∼2570, well below that of SF6 (24300), supporting further evaluation of CF3SCF3 as an alternative dielectric gas.
{"title":"Rate Coefficients for the OH Reaction with CF3SCF3: Atmospheric Lifetime and Global Warming Potential","authors":"Yue Liu,Miaoqing Li,Haotian Jiang,Weiqing Zhang,Hongwei Li,Xingan Wang,Jijun Zeng,Bo Zhao,Sheng Qin,Jian Lu,Xueming Yang,Wenrui Dong","doi":"10.1021/acs.jpclett.6c02727","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02727","url":null,"abstract":"Bis(trifluoromethyl) sulfide (CF3SCF3) is a candidate insulating gas whose atmospheric persistence is poorly constrained: the structure–activity relationship cannot be reliably extrapolated to this perfluorinated species, and the only available theoretical estimate has not yet been tested against experiment. We measured the rate coefficient of its dominant atmospheric loss, reaction with OH, by pulsed laser photolysis–laser-induced fluorescence over 272–328 K at 50 Torr. The reaction is slow and nearly temperature independent, with k1(298 K) = (2.15 ± 0.34) × 10–15 cm3 molecule–1 s–1 and a slight positive trend (apparent Ea = (0.30 ± 0.14) kcal mol–1). No O2 dependence was detectable at 50 Torr. The measured k1 exceeds the theoretical value by approximately an order of magnitude, implying an OH-initiated lifetime of ∼14.7 years and a 100-year GWP of ∼2570, well below that of SF6 (24300), supporting further evaluation of CF3SCF3 as an alternative dielectric gas.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"12 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221729","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}
Carbon–halogen bonds are central motifs in molecular chemistry, yet how a single C–X linkage behaves on an extended electron-accepting carbon framework remains poorly understood. Here, we combine negative ion photoelectron spectroscopy and theoretical calculations to investigate monohalogenated fullerene anions, C60X– (X = F, Cl, Br, and I), as gas-phase models for examining how local C–X bonding and cage-mediated electron stabilization jointly control electron detachment. From F to I, the C60–X interaction weakens systematically: the C–X bond length increases, orbital overlap decreases, and the excess electron evolves from mixed halogen–cage character in C60F–/C60Cl– to more halogen-centered character in C60Br–/C60I–. However, the electron detachment energies of C60X– lie within a narrow energy range of 3.5–3.7 eV, in contrast to isolated halide anions X–, whose electron detachment energies increase from F to Cl and then decrease from Cl to I. Energy decomposition analysis shows that this apparent contradiction arises from different stabilization of the neutral and anionic fullerene–halogen bonded states by the C60 cage. These results highlight fullerene-cage stabilization as a molecular design principle for stabilizing halogen-centered excess electrons and tuning the C–X bond activation in halogen-functionalized π-carbon materials.
{"title":"More Halogen-Localized, Yet More Strongly Electron Bound: Carbon Cage-Mediated Electron Stabilization in C60X– (X = F, Cl, Br, and I) Anions","authors":"Jianzhi Xu,Junda Li,Zhilong Wu,Hao Li,Zhen-Chao Long,Chang-Feng Zhu,Hong-Guang Xu,Wei-Jun Zheng,Xue-Bin Wang,Gao-Lei Hou","doi":"10.1021/acs.jpclett.6c02657","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02657","url":null,"abstract":"Carbon–halogen bonds are central motifs in molecular chemistry, yet how a single C–X linkage behaves on an extended electron-accepting carbon framework remains poorly understood. Here, we combine negative ion photoelectron spectroscopy and theoretical calculations to investigate monohalogenated fullerene anions, C60X– (X = F, Cl, Br, and I), as gas-phase models for examining how local C–X bonding and cage-mediated electron stabilization jointly control electron detachment. From F to I, the C60–X interaction weakens systematically: the C–X bond length increases, orbital overlap decreases, and the excess electron evolves from mixed halogen–cage character in C60F–/C60Cl– to more halogen-centered character in C60Br–/C60I–. However, the electron detachment energies of C60X– lie within a narrow energy range of 3.5–3.7 eV, in contrast to isolated halide anions X–, whose electron detachment energies increase from F to Cl and then decrease from Cl to I. Energy decomposition analysis shows that this apparent contradiction arises from different stabilization of the neutral and anionic fullerene–halogen bonded states by the C60 cage. These results highlight fullerene-cage stabilization as a molecular design principle for stabilizing halogen-centered excess electrons and tuning the C–X bond activation in halogen-functionalized π-carbon materials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"37 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221678","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 : 2026-10-20DOI: 10.1021/acs.jpclett.6c02778
Xuanyu Wang,Anan Wu,Sheng Hu
Proton transport through graphene is strongly affected by nanoscale morphology, yet the atomic pathway responsible for enhanced permeation near corrugations remains unclear. Here, using first-principles calculations, we resolve proton permeation pathways through individual hexagonal carbon rings in mechanically distorted graphene. We find that a single corrugation creates a heterogeneous permeation landscape in which different carbon rings exhibit substantially different barriers depending on their local strain and curvature, and the most highly curved region is not necessarily the most permeable. Analysis of the permeation energies shows that corrugation partially relieves local in-plane compression relative to planar graphene under the same imposed compression, thereby lowering the transition-state energy, while the remaining barrier variation among rings within the corrugation arises predominantly from the curvature-dependent stabilization of the adsorbed initial state. In addition, concave curvature produces particularly strong initial-state stabilization because the local orbital orientation enhances the interaction with the adsorbed proton. Consequently, weakly curved carbon rings can exhibit permeation barriers that are lower than those of more highly curved regions. These results show that proton transport through corrugated graphene is governed by the local balance between the transition-state accessibility associated with lattice deformation and curvature-induced stabilization of the adsorbed state.
{"title":"Competing Effects of Strain and Curvature on Proton Transport through Corrugated Graphene","authors":"Xuanyu Wang,Anan Wu,Sheng Hu","doi":"10.1021/acs.jpclett.6c02778","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02778","url":null,"abstract":"Proton transport through graphene is strongly affected by nanoscale morphology, yet the atomic pathway responsible for enhanced permeation near corrugations remains unclear. Here, using first-principles calculations, we resolve proton permeation pathways through individual hexagonal carbon rings in mechanically distorted graphene. We find that a single corrugation creates a heterogeneous permeation landscape in which different carbon rings exhibit substantially different barriers depending on their local strain and curvature, and the most highly curved region is not necessarily the most permeable. Analysis of the permeation energies shows that corrugation partially relieves local in-plane compression relative to planar graphene under the same imposed compression, thereby lowering the transition-state energy, while the remaining barrier variation among rings within the corrugation arises predominantly from the curvature-dependent stabilization of the adsorbed initial state. In addition, concave curvature produces particularly strong initial-state stabilization because the local orbital orientation enhances the interaction with the adsorbed proton. Consequently, weakly curved carbon rings can exhibit permeation barriers that are lower than those of more highly curved regions. These results show that proton transport through corrugated graphene is governed by the local balance between the transition-state accessibility associated with lattice deformation and curvature-induced stabilization of the adsorbed state.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221723","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 : 2026-10-20DOI: 10.1021/acs.jpclett.6c03178
Junjie Lai,Zhenli Xu,Huiming Xiong
Water-in-salt electrolytes are promising candidates for electrochemical devices. In this work, structures and dynamics of water-in-LiTFSI electrolytes are explored through large-scale atomistic molecular dynamics simulation employing a full-charge Drude polarizable force field with an O(N) -scaling random batch sum-of-Gaussians method for long-ranged electrostatic interactions. Disruption of the hydrogen bonding of bulk water and formation of LiTFSI networks in 21 m solution are observed. Particularly, the roles of cis and trans conformers of TFSI– are uncovered, and isomerization is found to occur in nanoseconds, on a similar time scale of Li+ escaping from the major cis-TFSI– conformers. Most water molecules are dynamically bound to Li+ with comparably rapid rotational motion in tens of picoseconds. Vehicular transport coupled to fast water dynamics and collective joining with the structural motion of Li+ along pathways of TFSI– cluster/network prevailed by cis-TFSI– are attributed to the appreciable Li+ conductivity in water-in-LiTFSI electrolytes.
{"title":"Water-Assisted Li+ Transport and cis-TFSI– Effects in Water-in-LiTFSI Electrolytes","authors":"Junjie Lai,Zhenli Xu,Huiming Xiong","doi":"10.1021/acs.jpclett.6c03178","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c03178","url":null,"abstract":"Water-in-salt electrolytes are promising candidates for electrochemical devices. In this work, structures and dynamics of water-in-LiTFSI electrolytes are explored through large-scale atomistic molecular dynamics simulation employing a full-charge Drude polarizable force field with an O(N) -scaling random batch sum-of-Gaussians method for long-ranged electrostatic interactions. Disruption of the hydrogen bonding of bulk water and formation of LiTFSI networks in 21 m solution are observed. Particularly, the roles of cis and trans conformers of TFSI– are uncovered, and isomerization is found to occur in nanoseconds, on a similar time scale of Li+ escaping from the major cis-TFSI– conformers. Most water molecules are dynamically bound to Li+ with comparably rapid rotational motion in tens of picoseconds. Vehicular transport coupled to fast water dynamics and collective joining with the structural motion of Li+ along pathways of TFSI– cluster/network prevailed by cis-TFSI– are attributed to the appreciable Li+ conductivity in water-in-LiTFSI electrolytes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"414 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221721","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 : 2026-10-20DOI: 10.1021/acs.jpclett.6c02808
Anam Fatima,Danielle Rosenberger,YongLe He,James N. Iuliano,Gregory M. Greetham,Partha Malakar,Andras Lukacs,Peter J. Tonge,Stephen R. Meech
Positive reversibly switchable fluorescent proteins (+rsFPs) are genetically encoded fluorescent labels allowing super-resolution microscopy without the fading inherent in the better established negative (−) rsFPs. Typically, switching is initiated by an ultrafast excited-state isomerization reaction. Here, we investigate the ultrafast photophysics of four structurally similar variants of the archetypal +rsFP Padron, including Padron0.9, Padron2, Kohinoor, and a newly reported “reverse” Kohinoor mutant (Kohinoor S176F) using ultrafast optical and vibrational spectroscopy. Padron0.9 exhibits an efficient excited-state proton transfer (ESPT) reaction in parallel with photoisomerization, whereas Kohinoor and Padron2 do not. Remarkably, introducing the single reverse mutation S176F in Kohinoor restores Padron-like ESPT dynamics, even though the mutation is remote from the proton donor. This result demonstrates that a single amino acid residue near to, but not in direct H-bonded interaction with, the chromophore can govern the fate of excited states. TRIR measurements reveal distinct changes in the local hydrogen-bonding network and chromophore–protein interactions associated with ESPT-active variants and further reveal a key role for H-bonding between the chromophore and an arginine residue through a study of the R66K mutant of Padron0.9. Overall, these results show that subtle mutations shift the excited state between proton transfer and photoisomerization pathways, providing mechanistic insight into photoswitching in rsFPs, thus guiding the design of improved fluorescent proteins for superresolution bioimaging.
{"title":"Remote Control of Excited-State Chemistry in Positive Reversibly Switchable Fluorescent Proteins","authors":"Anam Fatima,Danielle Rosenberger,YongLe He,James N. Iuliano,Gregory M. Greetham,Partha Malakar,Andras Lukacs,Peter J. Tonge,Stephen R. Meech","doi":"10.1021/acs.jpclett.6c02808","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02808","url":null,"abstract":"Positive reversibly switchable fluorescent proteins (+rsFPs) are genetically encoded fluorescent labels allowing super-resolution microscopy without the fading inherent in the better established negative (−) rsFPs. Typically, switching is initiated by an ultrafast excited-state isomerization reaction. Here, we investigate the ultrafast photophysics of four structurally similar variants of the archetypal +rsFP Padron, including Padron0.9, Padron2, Kohinoor, and a newly reported “reverse” Kohinoor mutant (Kohinoor S176F) using ultrafast optical and vibrational spectroscopy. Padron0.9 exhibits an efficient excited-state proton transfer (ESPT) reaction in parallel with photoisomerization, whereas Kohinoor and Padron2 do not. Remarkably, introducing the single reverse mutation S176F in Kohinoor restores Padron-like ESPT dynamics, even though the mutation is remote from the proton donor. This result demonstrates that a single amino acid residue near to, but not in direct H-bonded interaction with, the chromophore can govern the fate of excited states. TRIR measurements reveal distinct changes in the local hydrogen-bonding network and chromophore–protein interactions associated with ESPT-active variants and further reveal a key role for H-bonding between the chromophore and an arginine residue through a study of the R66K mutant of Padron0.9. Overall, these results show that subtle mutations shift the excited state between proton transfer and photoisomerization pathways, providing mechanistic insight into photoswitching in rsFPs, thus guiding the design of improved fluorescent proteins for superresolution bioimaging.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"24 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221720","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}
Upscaling perovskite solar cells (PSCs) for large-area industrial manufacturing urgently demands efficient and scalable surface passivation strategies. Although blade coating is highly promising for device upscaling, achieving comprehensive surface passivation remains a key challenge due to the abundant defects inherent in blade-coated perovskite films. Herein, we present a synergistic surface modification strategy combining dimensional engineering with passivation engineering for blade-coated PSCs. We introduce a multifunctional group Lewis base passivator, 5-bromobenzo[b]thiophen-3(2H)-one (BTO), to complement traditional dimensional engineering (e.g., phenethylammonium iodide (PEAI)), which typically struggles to passivate deep-level defects. In this dual strategy, PEAI constructs a robust 2D/3D heterojunction for interfacial energy level alignment, while BTO passivates uncoordinated Pb2+ defects via synergistic dual-site coordination. Consequently, blade-coated PSCs exhibit a power conversion efficiency of 25.15% and maintain 92.7% of their initial efficiency after 1500 h of air exposure (25 °C, 20–30% RH). Furthermore, this strategy mitigates efficiency roll-off upon scaling, yielding a high PCE of 22.02% for 14.7 cm2 minimodules.
{"title":"Synergistic Dimensional and Passivation Engineering via Blade Coating Enables Efficient and Stable Perovskite Solar Cells","authors":"Junhao Geng,Yulu Liu,Xiao Zhou,Liu Yang,Shuang Li,Hongmei Zhan,Helong Zhu,Dezhong Zhang,Hui Tong,Zhipeng Wei,Chuanjiang Qin","doi":"10.1021/acs.jpclett.6c02871","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02871","url":null,"abstract":"Upscaling perovskite solar cells (PSCs) for large-area industrial manufacturing urgently demands efficient and scalable surface passivation strategies. Although blade coating is highly promising for device upscaling, achieving comprehensive surface passivation remains a key challenge due to the abundant defects inherent in blade-coated perovskite films. Herein, we present a synergistic surface modification strategy combining dimensional engineering with passivation engineering for blade-coated PSCs. We introduce a multifunctional group Lewis base passivator, 5-bromobenzo[b]thiophen-3(2H)-one (BTO), to complement traditional dimensional engineering (e.g., phenethylammonium iodide (PEAI)), which typically struggles to passivate deep-level defects. In this dual strategy, PEAI constructs a robust 2D/3D heterojunction for interfacial energy level alignment, while BTO passivates uncoordinated Pb2+ defects via synergistic dual-site coordination. Consequently, blade-coated PSCs exhibit a power conversion efficiency of 25.15% and maintain 92.7% of their initial efficiency after 1500 h of air exposure (25 °C, 20–30% RH). Furthermore, this strategy mitigates efficiency roll-off upon scaling, yielding a high PCE of 22.02% for 14.7 cm2 minimodules.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"13 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218900","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 : 2026-10-20DOI: 10.1021/acs.jpclett.6c02865
Jingyue Wang,Jian Zhang,Xueying Li,Xin Lin,Wenqi Wang,Zhubin Hu,Xue-Bin Wang,Zhenrong Sun,Yan Yang
Characterization of Au(II) oxidation state remains challenging because d9 Au(II) complexes readily disproportionate to Au(I) and Au(III). We report the first high-resolution cryogenic photoelectron spectroscopic characterization of an isolated mononuclear Au(II) halide anion, AuCl3–, combining cryogenic anion photoelectron spectroscopy (PES) with relativistic quantum chemical calculations. The measured adiabatic detachment energy (ADE) and vertical detachment energy (VDE) are 4.63 ± 0.04 and 4.93 ± 0.04 eV, respectively. The VDE shows a near-plateau relative to AuCl2– upon adding an electronegative chlorine ligand, deviating from conventional superhalogen trends. Electronic-structure analysis reveals a high-energy Au 5d σ-antibonding frontier orbital, its unpaired electron axially localized in the Jahn–Teller-distorted C2v structure. Comparative relativistic vs nonrelativistic calculations confirm relativistic effects suppressing the VDE increase from AuCl2– to AuCl3–. The disproportionation reaction 2AuCl3– → AuCl2– + AuCl4– is downhill by 1.48 eV. These results connect relativistic electronic structure, photodetachment energetics, and Au(II)’s electronic lability and disproportionation tendency.
{"title":"Direct Spectroscopic Benchmark of Isolated Au(II) Oxidation State: Electronic Structure and Instability of AuCl3–","authors":"Jingyue Wang,Jian Zhang,Xueying Li,Xin Lin,Wenqi Wang,Zhubin Hu,Xue-Bin Wang,Zhenrong Sun,Yan Yang","doi":"10.1021/acs.jpclett.6c02865","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02865","url":null,"abstract":"Characterization of Au(II) oxidation state remains challenging because d9 Au(II) complexes readily disproportionate to Au(I) and Au(III). We report the first high-resolution cryogenic photoelectron spectroscopic characterization of an isolated mononuclear Au(II) halide anion, AuCl3–, combining cryogenic anion photoelectron spectroscopy (PES) with relativistic quantum chemical calculations. The measured adiabatic detachment energy (ADE) and vertical detachment energy (VDE) are 4.63 ± 0.04 and 4.93 ± 0.04 eV, respectively. The VDE shows a near-plateau relative to AuCl2– upon adding an electronegative chlorine ligand, deviating from conventional superhalogen trends. Electronic-structure analysis reveals a high-energy Au 5d σ-antibonding frontier orbital, its unpaired electron axially localized in the Jahn–Teller-distorted C2v structure. Comparative relativistic vs nonrelativistic calculations confirm relativistic effects suppressing the VDE increase from AuCl2– to AuCl3–. The disproportionation reaction 2AuCl3– → AuCl2– + AuCl4– is downhill by 1.48 eV. These results connect relativistic electronic structure, photodetachment energetics, and Au(II)’s electronic lability and disproportionation tendency.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"14 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221722","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}
Unveiling the microstructural evolution of the active sites in reaction atmospheres is the basis of catalytic reaction mechanisms. Herein, the Pt clusters confined within mordenite (MOR) in ammonia and hydrogen atmospheres are investigated with both first-principles calculations and experiments. The thermodynamic states of Ptn clusters (n = 1–7) in NH3 and H2 atmospheres, both in gas phase and MOR channels, are systematically investigated using ab initio thermodynamics. Theoretical results reveal that smaller Ptn clusters remain stable in an NH3 atmosphere due to strong Pt–NH3 coordination, which promotes cluster dispersion. In contrast, H2 favors the formation of slightly larger clusters by acting as a double-edged sword: H inserts into the Pt–Pt bonds while simultaneously serving as a bridge to stabilize the cluster. Control experiments confirm that treatment with NH3 and H2 redisperses Pt clusters in MOR, with NH3 treatment exhibiting superior dispersion performance characterized by aberration-corrected scanning transmission electron microscopy.
{"title":"Structural Evolution of Mordenite-Supported Pt Clusters in Ammonia and Hydrogen Atmospheres","authors":"Chengkai Jin,Runping Ye,Tong Guan,Xiaohu Yu,Qing Liu,Xunhua Zhao,Qiang Li,Gang Feng","doi":"10.1021/acs.jpclett.6c02769","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02769","url":null,"abstract":"Unveiling the microstructural evolution of the active sites in reaction atmospheres is the basis of catalytic reaction mechanisms. Herein, the Pt clusters confined within mordenite (MOR) in ammonia and hydrogen atmospheres are investigated with both first-principles calculations and experiments. The thermodynamic states of Ptn clusters (n = 1–7) in NH3 and H2 atmospheres, both in gas phase and MOR channels, are systematically investigated using ab initio thermodynamics. Theoretical results reveal that smaller Ptn clusters remain stable in an NH3 atmosphere due to strong Pt–NH3 coordination, which promotes cluster dispersion. In contrast, H2 favors the formation of slightly larger clusters by acting as a double-edged sword: H inserts into the Pt–Pt bonds while simultaneously serving as a bridge to stabilize the cluster. Control experiments confirm that treatment with NH3 and H2 redisperses Pt clusters in MOR, with NH3 treatment exhibiting superior dispersion performance characterized by aberration-corrected scanning transmission electron microscopy.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"73 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218902","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}
Suppressing dark current while preserving charge extraction and bandwidth remains a key challenge for organic photodetectors (OPDs), because conventional carrier-blocking strategies often compromise photocarrier transport. Here, we report a morphology-driven strategy based on water-bath-assisted self-assembly of poly(3-hexylthiophene) (P3HT) nanowires in a single-layer donor–acceptor bulk heterojunction. These preassembled nanowires direct vertical phase separation of the blend, creating a morphology-controlled carrier-injection pathway that suppresses leakage current under reverse bias while retaining efficient photocarrier extraction. Spectroscopic analyses reveal that nanowire formation redistributes the donor–acceptor components along the vertical direction, creating an energetically favorable architecture that blocks undesired carrier injection while maintaining directional charge transport. As a result, the fabricated photovoltaic-type photodetectors exhibit a shot-noise-limited specific detectivity (D*sh) of 1.50 × 1012 jones, a linear dynamic range (LDR) of 144.2 dB, and a −3 dB cutoff frequency of 4.94 MHz. Additionally, the ZnO-modified photoconductive device yields a D*sh of 1.90 × 1013 jones and an LDR up to 160.1 dB while preserving an 8.45 MHz bandwidth, achieving state-of-the-art performance across both photovoltaic and photoconductive OPD architectures. This work establishes nanowire-induced vertical phase separation as a morphology-design principle for regulating carrier injection in organic optoelectronic devices, providing new insights into simultaneously achieving suppressed dark current, wide dynamic range and multimegahertz bandwidth in simplified device architectures.
{"title":"Nanowire-Induced Vertical Phase Separation Enables Dark-Current Suppression and High Bandwidth in Single-Layer Organic Photodetectors","authors":"Yadan Deng,Xinmu Chen,Jingzan Jiang,Jia Li,Xiaolong Li,Yali Yu,Jiayang Jiang,Yu Zhang,Zhidong Lou,Yufeng Hu,Feng Teng","doi":"10.1021/acs.jpclett.6c03056","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c03056","url":null,"abstract":"Suppressing dark current while preserving charge extraction and bandwidth remains a key challenge for organic photodetectors (OPDs), because conventional carrier-blocking strategies often compromise photocarrier transport. Here, we report a morphology-driven strategy based on water-bath-assisted self-assembly of poly(3-hexylthiophene) (P3HT) nanowires in a single-layer donor–acceptor bulk heterojunction. These preassembled nanowires direct vertical phase separation of the blend, creating a morphology-controlled carrier-injection pathway that suppresses leakage current under reverse bias while retaining efficient photocarrier extraction. Spectroscopic analyses reveal that nanowire formation redistributes the donor–acceptor components along the vertical direction, creating an energetically favorable architecture that blocks undesired carrier injection while maintaining directional charge transport. As a result, the fabricated photovoltaic-type photodetectors exhibit a shot-noise-limited specific detectivity (D*sh) of 1.50 × 1012 jones, a linear dynamic range (LDR) of 144.2 dB, and a −3 dB cutoff frequency of 4.94 MHz. Additionally, the ZnO-modified photoconductive device yields a D*sh of 1.90 × 1013 jones and an LDR up to 160.1 dB while preserving an 8.45 MHz bandwidth, achieving state-of-the-art performance across both photovoltaic and photoconductive OPD architectures. This work establishes nanowire-induced vertical phase separation as a morphology-design principle for regulating carrier injection in organic optoelectronic devices, providing new insights into simultaneously achieving suppressed dark current, wide dynamic range and multimegahertz bandwidth in simplified device architectures.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"42 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218949","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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