The Journal of Physical Chemistry Letters最新文献_第7页

Cooperative Relaxation Governs the Viscosity of Ionic Liquids 协同弛豫支配离子液体的粘度

IF 4.5 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-10-15 Epub Date: 2026-10-01 DOI: 10.1021/acs.jpclett.6c02640

Shurui Miao, Bela Farago, Ingo Hoffmann, Rob Atkin, Michael Gradzielski, Gregory G. Warr

{"title":"Cooperative Relaxation Governs the Viscosity of Ionic Liquids","authors":"Shurui Miao, Bela Farago, Ingo Hoffmann, Rob Atkin, Michael Gradzielski, Gregory G. Warr","doi":"10.1021/acs.jpclett.6c02640","DOIUrl":"10.1021/acs.jpclett.6c02640","url":null,"abstract":"Ionic liquids are promising solvents for batteries, biomassprocessingand critical mineral recovery, but their viscosities can exceed thoseof conventional molecular solvents by several orders of magnitude,impeding mass and charge transport and complicating process design.Using complementary neutron spin echo spectroscopy and nuclear magneticresonance diffusometry, we probe local and long-range dynamics ofthree protic ionic liquids over time scales from 10–12 to 10–3 seconds. We identify a fast relaxationwith closely corresponding self and collective time scales, indicatingcooperative rearrangement of the surrounding molecular network. Itscharacteristic time scale correlates with bulk viscosity, while itstemperature dependence reveals distinct Arrhenius activation energiesdepending on whether extended networks are dominated by hydrogen bondingor electrostatic interactions. These results link cooperative networkrelaxation to macroscopic viscosity and show how molecular structurecan tune the energetic cost of structural relaxation through networkconnectivity.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11778–11783"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090593","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}

引用次数: 0

Limits of Memory-Assisted Coherence in Cavity-Embedded Molecules 空腔嵌入分子中记忆辅助相干性的局限性

IF 4.5 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-10-15 Epub Date: 2026-10-05 DOI: 10.1021/acs.jpclett.6c02396

Joshua C. Kinslow, Ben S. Humphries, Dale Green, Magnus O. Borgh, Garth A. Jones

{"title":"Limits of Memory-Assisted Coherence in Cavity-Embedded Molecules","authors":"Joshua C. Kinslow, Ben S. Humphries, Dale Green, Magnus O. Borgh, Garth A. Jones","doi":"10.1021/acs.jpclett.6c02396","DOIUrl":"10.1021/acs.jpclett.6c02396","url":null,"abstract":"Strong light–matter coupling in optical cavitiesis beingwidely explored as a strategy for modifying molecular dynamics andenhancing coherence. At the same time, structured vibrational environmentscan exhibit non-Markovian memory that promotes information backflowand coherence revival. We investigate the competition between theseeffects in a vibronic molecular system strongly coupled to a lossyoptical cavity. Using hierarchical equations of motion to treat structuredvibrational baths, we quantify both system coherence and non-Markovianityvia the l1 norm of coherence and the Breuer–Laine–Piilomeasure, respectively. We find that cavity coupling enhances coherencein overdamped environments but can suppress memory-assisted coherencein resonant underdamped regimes, even in the absence of significantphoton loss. This suppression arises from hybridization-induced modificationof system–bath information flow. We demonstrate that cavitycoupling does not universally protect coherence but establishes limitsgoverned by the competition between vibrational recurrence time scalesand polaritonic hybridization.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11723–11730"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092276","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}

引用次数: 0

Formation of Carbonisocyanatidic Amide in Interstellar Ice Analogs as a Candidate Precursor to Prebiotic Pyrimidines 星际类似物中碳异氰酸酯酰胺作为益生元嘧啶的候选前体的形成

IF 4.5 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-10-15 Epub Date: 2026-10-05 DOI: 10.1021/acs.jpclett.6c02249

Xilin Bai, Jinghui Lu, Baoyu Song, Jiuzhong Yang, Yang Pan, Zhibiao Li, Cheng Zhu, Zhubin Hu, Haitao Sun, Zhenrong Sun, Ralf I. Kaiser, Tao Yang

{"title":"Formation of Carbonisocyanatidic Amide in Interstellar Ice Analogs as a Candidate Precursor to Prebiotic Pyrimidines","authors":"Xilin Bai, Jinghui Lu, Baoyu Song, Jiuzhong Yang, Yang Pan, Zhibiao Li, Cheng Zhu, Zhubin Hu, Haitao Sun, Zhenrong Sun, Ralf I. Kaiser, Tao Yang","doi":"10.1021/acs.jpclett.6c02249","DOIUrl":"10.1021/acs.jpclett.6c02249","url":null,"abstract":"Understanding how pyrimidine nucleobases form in spaceis centralto prebiotic chemistry, yet the pathways assembling these heterocyclesremain unresolved. Carbonisocyanatidic amide (H2NC(O)NCO),an acyclic intermediate with heteroatom connectivity relevant to uraciland thymine, has not been detected in interstellar ice analogs. Here,we show that carbonisocyanatidic amide is formed in low-temperatureisocyanic acid (HNCO) ices exposed to energetic electrons and is identifiedduring the desorption phase by synchrotron vacuum ultraviolet photoionizationreflectron time-of-flight mass spectrometry combined with high-levelquantum chemical calculations. A plausible, product-constrained networkinvolves hydrogen abstraction and addition steps that generate radicalintermediates, followed by radical–radical recombination andcarbon–nitrogen bond formation. These results establish anexperimental link between simple interstellar volatiles and nitrogen-richmolecular architectures relevant to pyrimidine nucleobases, supportingan astrochemical route to prebiotic intermediates in icy grains andtheir possible delivery to early Earth.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11906–11914"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090900","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}

引用次数: 0

Highly Controllable Polarity in Two-Dimensional Vertical Transistors 二维垂直晶体管的高度可控极性

IF 4.5 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-10-15 Epub Date: 2026-10-03 DOI: 10.1021/acs.jpclett.6c02965

Likuan Ma, Quanyang Tao, Lingan Kong, Wanrong Liu, Chenxing Jin, Xiaofang Shi, Ruihan Li, Guansong Qiu, Yuan Liu, Jia Sun, Junliang Yang

{"title":"Highly Controllable Polarity in Two-Dimensional Vertical Transistors","authors":"Likuan Ma, Quanyang Tao, Lingan Kong, Wanrong Liu, Chenxing Jin, Xiaofang Shi, Ruihan Li, Guansong Qiu, Yuan Liu, Jia Sun, Junliang Yang","doi":"10.1021/acs.jpclett.6c02965","DOIUrl":"10.1021/acs.jpclett.6c02965","url":null,"abstract":"Two-dimensional (2D) vertical transistors, featuringatomicallythin channels and an inherent vertical architecture, hold extensivepromise for ultrascaled electronics. However, achieving reliable polaritycontrol in such devices has remained a persistent challenge over thepast decade. Here, we demonstrate a vertical MoTe2 transistorwith highly controllable polarity. By implementing van der Waals (vdW)integration for both contacts, the carrier injection barrier can beeffectively modulated via the work functions of the electrodes. Leveragingthe favorable band alignment with graphene and the narrow bandgapof MoTe2, we achieve selective n-type and p-type operationusing Ag and Pt top contacts, respectively. Furthermore, through graphenework-function engineering, we optimize the switching performance,realizing an on/off ratio exceeding 104 in a ∼5nm p-type MoTe2 vertical transistor, surpassing all previouslyreported p-type 2D vertical transistors based on graphene/TMD/metalarchitectures. Finally, we integrate two vertical transistors of oppositepolarities, fabricated from graphene/MoTe2 heterostructurewith different top contacts, to demonstrate a complementary inverteron a single chip. Our work not only provides a viable strategy forpolarity control in vertical heterostructures but also suggests apotential pathway toward complementary circuits based on 2D verticaltransistors.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11829–11835"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090901","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}

引用次数: 0

Water Activity Governs Ice Nanocrystal Evolution in Rapidly Frozen Sugar Solutions 在速冻糖溶液中，水的活性支配着冰纳米晶的演化

IF 4.5 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-10-15 Epub Date: 2026-10-05 DOI: 10.1021/acs.jpclett.6c02690

Takayuki Kumada, Rintaro Nakabe, Hiroshi Nakagawa, Yoshinobu Hirata, Takumi Mochizuki, Ryuhei Motokawa, Katsuaki Kodama, Kosuke Hiroi, Takayuki Oku, Kazuki Ohishi, Toshiaki Morikawa, Yukihiko Kawamura, Kiyoshi Kawai, Yoshiharu Suzuki

{"title":"Water Activity Governs Ice Nanocrystal Evolution in Rapidly Frozen Sugar Solutions","authors":"Takayuki Kumada, Rintaro Nakabe, Hiroshi Nakagawa, Yoshinobu Hirata, Takumi Mochizuki, Ryuhei Motokawa, Katsuaki Kodama, Kosuke Hiroi, Takayuki Oku, Kazuki Ohishi, Toshiaki Morikawa, Yukihiko Kawamura, Kiyoshi Kawai, Yoshiharu Suzuki","doi":"10.1021/acs.jpclett.6c02690","DOIUrl":"10.1021/acs.jpclett.6c02690","url":null,"abstract":"Formation and evolutionof ice nanocrystals in rapidlyfrozen sugarsolutions were investigated using spin-contrast-variation small-angleneutron scattering (SCV-SANS). As the sugar concentration decreased,the SCV-SANS signal from nanocrystalline ice plates decreased relativeto that from micrometer-sized ice crystals, while the diffractionpeaks became sharper. These results indicate that the micrometer-sizedcrystals formed predominantly through Ostwald ripening, which dependedprimarily on sugar concentration and secondarily on sugar species.Regardless of the initial sugar concentration, ice crystal growthwas arrested when the sugar concentration in the freeze-concentratedamorphous ice reached 66–71 wt % for trehalose and sucroseand 62–63 wt % for glucose. Despite its lower glass-transitiontemperature, glucose showed growth arrest at a lower degree of freezeconcentration than trehalose and sucrose. However, the water activityat these growth-arrest concentrations converged to 0.80–0.82under the present rapid-freezing conditions, indicating that wateractivity determines ice nanocrystal evolution until vitrificationarrests further growth.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 41","pages":"11784–11791"},"PeriodicalIF":4.5,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091536","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}

引用次数: 0

Broadband TransientFluorescence Reveals a Two-StatePicture of Peridinin 宽频带瞬态荧光显示橄榄素的双态图像

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-10-14 DOI: 10.1021/acs.jpclett.6c02559

Alina Bach,Constantin Jaschke,Heyuan Liu,Hailong Chen,Erika Keil,Eckhard Hofmann,Yuxiang Weng,Jan P. Götze,Benjamin P. Fingerhut,Jürgen Hauer

{"title":"Broadband Transient\u0000Fluorescence Reveals a Two-State\u0000Picture of Peridinin","authors":"Alina Bach,Constantin Jaschke,Heyuan Liu,Hailong Chen,Erika Keil,Eckhard Hofmann,Yuxiang Weng,Jan P. Götze,Benjamin P. Fingerhut,Jürgen Hauer","doi":"10.1021/acs.jpclett.6c02559","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02559","url":null,"abstract":"Abstract Peridinin is a light-harvesting apocarotenoid whose excited-state relaxation is often described by population transfer among 1Bu, 2Ag, and intramolecular charge-transfer states. Here broadband-detected transient fluorescence reveals a simpler picture for peridinin in ethylene glycol. Following optical excitation, we observe instantaneous blue-green emission from the bright 1Bu state that depopulates with a 150 fs time constant and directly gives rise to weak red emission from the lowest 2Ag state, which decays in 12 ps. The presence of an isosbestic point and the absence of additional fluorescence components indicate direct internal conversion without a resolvable hot S1 or a separate equilibration process involving a charge-transfer state. XMS-RASPT2 and DFT/MRCI calculations reproduce this behavior by showing strong displacement of the 1Bu and 2Ag minima from the Franck–Condon region and weak oscillator strength at the relaxed 2Ag minimum. The results identify peridinin as an emitter from its 1Bu and 2Ag states and revise the interpretation of its charge-transfer-like signatures.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"482 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209841","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}

引用次数: 0

BarrierlessGas-Phase Formation of the Phenyl Radical(C6H5, X2A1) via AtomicCarbon Induced Ring Expansion–A Versatile Framework to HückelAromatic Aryl Radicals in Molecular Clouds 苯基自由基（C6H5, X2A1）通过原子碳诱导的环扩张无阻碍气相形成——分子云中<s:1>烷基芳基自由基的通用框架

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-10-14 DOI: 10.1021/acs.jpclett.6c03038

Daniel González,Ashleigh G. Hartwig,Surajit Metya,Iakov A. Medvedkov,Shane J. Goettl,Alexander M. Mebel,Ralf I. Kaiser

{"title":"Barrierless\u0000Gas-Phase Formation of the Phenyl Radical\u0000(C6H5, X2A1) via Atomic\u0000Carbon Induced Ring Expansion–A Versatile Framework to Hückel\u0000Aromatic Aryl Radicals in Molecular Clouds","authors":"Daniel González,Ashleigh G. Hartwig,Surajit Metya,Iakov A. Medvedkov,Shane J. Goettl,Alexander M. Mebel,Ralf I. Kaiser","doi":"10.1021/acs.jpclett.6c03038","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c03038","url":null,"abstract":"Abstract The low-temperature formation of aromatic molecules in the interstellar medium remains a major challenge in astrochemistry. Here, crossed molecular beam experiments combined with high-level electronic structure and Rice–Ramsperger–Kassel–Marcus (RRKM) calculations reveal the barrierless formation of the simplest aryl radical, the 6π Hückel aromatic phenyl radical (C6H5•), through the reaction of ground-state atomic carbon with 1,3-cyclopentadiene (c-C5H6). The reaction proceeds via carbon addition, ring expansion, hydrogen atom elimination, and aromatization, with all transition states lying below the energy of the separated reactants. The measured reaction exoergicity agrees with theory, rendering the reaction operative even in the coldest interstellar environments. More broadly, carbon-atom-induced ring-expansion can transform cyclopentadiene motifs embedded within larger polycyclic aromatic hydrocarbons into aryl radical centers, providing a previously unrecognized route to aromatic molecular growth. These findings establish carbon-atom-mediated skeletal editing as a viable low-temperature mechanism for building increasingly complex aromatic carbonaceous molecules in space.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"32 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209259","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}

引用次数: 0

Robust MeltingDepression in Cu–Ag DespiteEndothermic Mixing 尽管吸热混合，Cu-Ag中强劲的熔化抑制

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-10-14 DOI: 10.1021/acs.jpclett.6c02759

Christopher M. Andolina,Wissam A. Saidi

{"title":"Robust Melting\u0000Depression in Cu–Ag Despite\u0000Endothermic Mixing","authors":"Christopher M. Andolina,Wissam A. Saidi","doi":"10.1021/acs.jpclett.6c02759","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02759","url":null,"abstract":"Abstract Cu–Ag exhibits a melting depression despite endothermic mixing and limited solid solubility. We combine density functional theory (DFT), machine-learning interatomic potentials, and large-scale two-phase coexistence simulations to resolve its composition-dependent melting, energetics, density, and transport. The lowest sampled fixed-composition coexistence temperature is 970 ± 3 K at 45 at. % Cu, while the maximum end point-referenced depression is 328.9 ± 2.5 K at 55 at. % Cu. The depression persists across ordered solids and prescribed solid–liquid composition partitions, with partitioning-induced shifts remaining modest relative to the depression. Intermediate composition solids incur a larger energetic penalty than the endothermically mixed liquid, providing an energetic basis for the melting depression without requiring favorable liquid mixing. PBE and PBEsol alter absolute melting temperatures, densities, and diffusivities but yield nearly identical maximum end point-referenced depressions. The depression is therefore robust to chemical ordering and functional choice, while its equilibrium depth depends on explicit solid–liquid compositional partitioning.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"52 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209844","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}

引用次数: 0

Pressure-Driven Cooperative Intermolecular–CovalentBond Relaxation in a Hydrogen-Bonded Organic Framework 氢键有机骨架中压力驱动的协同分子间共价键弛豫

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-10-14 DOI: 10.1021/acs.jpclett.6c02700

Yong Zhou,Hengxin Fang,Aiping Yang,Zhaoyang Zheng,Changqing Sun

{"title":"Pressure-Driven Cooperative Intermolecular–Covalent\u0000Bond Relaxation in a Hydrogen-Bonded Organic Framework","authors":"Yong Zhou,Hengxin Fang,Aiping Yang,Zhaoyang Zheng,Changqing Sun","doi":"10.1021/acs.jpclett.6c02700","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02700","url":null,"abstract":"Abstract Ordered hydrogen-bond networks provide crystalline organic materials with structural adaptability, yet how compression is distributed between intermolecular hydrogen bonds and intramolecular donor covalent bonds remains unclear. Here, we combine in situ high-pressure Raman spectroscopy and first-principles calculations to resolve the bond-specific pressure response of a melamine–cyanuric acid hydrogen-bonded organic framework (M–CA HOF). Between 1.04 and 8.35 GPa, the low-frequency mode predominantly associated with the N–H···N motif hardens, whereas the N–H···O-associated mode shows little net change; two N–H stretching modes shift to lower wavenumber. Calculations relate these opposite responses to concurrent shortening and bond-order gain of the H···N/H···O and elongation/bond-order loss of the connected N–H bonds, accompanied by hydrogen-bond angular adjustment and local electronic redistribution. These results support a cooperative intermolecular–covalent relaxation mechanism through which an ordered hydrogen-bond network accommodates compression by correlated local-bond adjustments.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"11 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209261","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}

引用次数: 0

Signatures ofBand-like Charge Carrier Transport ina Three-Dimensional Fe-HHTP Metal–Organic Framework 三维Fe-HHTP金属-有机骨架中带状电荷载流子输运的特征

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2026-10-14 DOI: 10.1021/acs.jpclett.6c03062

Md Soif Ahmed,Marina I. Schönherr,Marco Ballabio,Sandra M. Estévez,Mariela Menghini,Dana D. Medina,Enrique Cánovas

{"title":"Signatures of\u0000Band-like Charge Carrier Transport in\u0000a Three-Dimensional Fe-HHTP Metal–Organic Framework","authors":"Md Soif Ahmed,Marina I. Schönherr,Marco Ballabio,Sandra M. Estévez,Mariela Menghini,Dana D. Medina,Enrique Cánovas","doi":"10.1021/acs.jpclett.6c03062","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c03062","url":null,"abstract":"Abstract Metal–organic frameworks (MOFs) offer exceptional structural and chemical tunability, and the emergence of electrically conductive variants creates new opportunities for functional optoelectronic materials. Here, we investigate charge transport in a three-dimensional (3D) Fe-HHTP MOF (or Fe-CAU-42), composed of hexahydroxytriphenylene (HHTP)-based supertetrahedral units and trimeric Fe(III) oxo cluster nodes arranged in a diamond structure. Temperature dependent Van der Pauw (vdP) electrical conductivity measurements reveal an Arrhenius-type thermally activated charge transport mechanism operating in pelletized samples. Terahertz time-domain spectroscopy is used to probe the frequency-resolved complex conductivity of the Fe-HHTP pellet. The THz conductivity spectra are well-described by the Drude–Smith model, indicating the presence of mobile charge carriers with band-like dynamics subject to backscattering and localization. Temperature-dependent conductivity analysis reveals that the increase in conductivity with temperature is governed primarily by changes in carrier density rather than by changes in scattering time (and hence mobility). DC conductivities ranging from 6.54 × 10–3 S cm–1 at 300 K to 1.22 × 10–3 S cm–1 at 77 K are extracted from modeling of the THz data, in excellent agreement with van der Pauw measurements. The combined results establish a transport picture in which charge motion is dominated by localized band-like charge carriers with thermally activated carrier density, providing direct insight into carrier dynamics in conductive 3D catecholate MOFs.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"292 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209262","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}

引用次数: 0