The Journal of Physical Chemistry C最新文献

{"title":"Dominating Role of Carrier Localization over Griffiths Inhomogeneity and Phase Separation on Magnetoresistance in High Entropy Manganites","authors":"Radhamadhab Das, Sujan Sen, Shreyashi Chowdhury, Sudipa Bhattacharya, Sudisha Mondal, Tapas Kumar Mandal, Arup Gayen, Vasundhara Mutta, Md. Motin Seikh","doi":"10.1021/acs.jpcc.4c07154","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07154","url":null,"abstract":"The colossal magnetoresistance (CMR) and metal–insulator transitions in electronically correlated manganite oxides are well-known to be driven and improved by coexisting magneto-electronic phases of competitive origin. Such magneto-electronic inhomogeneity or the so-called phase-separated state appears when several physical interactions are simultaneously active. This makes doped manganites extremely sensitive to the parameters like the nature and extent of doping, A-site cation radius (<i></i><span style=\"color: inherit;\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\" display=\"inline\" overflow=\"scroll\"><mo stretchy=\"false\">⟨</mo><msub><mi>r</mi><mi>A</mi></msub><mo stretchy=\"false\">⟩</mo></math>' role=\"presentation\" style=\"position: relative;\" tabindex=\"0\"><nobr aria-hidden=\"true\"><span overflow=\"scroll\" style=\"width: 1.935em; display: inline-block;\"><span style=\"display: inline-block; position: relative; width: 1.764em; height: 0px; font-size: 110%;\"><span style=\"position: absolute; clip: rect(1.651em, 1001.71em, 2.957em, -999.997em); top: -2.554em; left: 0em;\"><span><span style=\"font-family: STIXMathJax_Main;\">⟨</span><span><span style=\"display: inline-block; position: relative; width: 0.969em; height: 0px;\"><span style=\"position: absolute; clip: rect(3.355em, 1000.4em, 4.151em, -999.997em); top: -3.974em; left: 0em;\"><span style=\"font-family: STIXMathJax_Normal-italic;\">𝑟</span><span style=\"display: inline-block; width: 0px; height: 3.98em;\"></span></span><span style=\"position: absolute; top: -3.804em; left: 0.401em;\"><span style=\"font-size: 70.7%; font-family: STIXMathJax_Normal-italic;\">𝐴</span><span style=\"display: inline-block; width: 0px; height: 3.98em;\"></span></span></span></span><span style=\"font-family: STIXMathJax_Main;\">⟩</span></span><span style=\"display: inline-block; width: 0px; height: 2.56em;\"></span></span></span><span style=\"display: inline-block; overflow: hidden; vertical-align: -0.309em; border-left: 0px solid; width: 0px; height: 1.128em;\"></span></span></nobr><span role=\"presentation\"><math display=\"inline\" overflow=\"scroll\" xmlns=\"http://www.w3.org/1998/Math/MathML\"><mo stretchy=\"false\">⟨</mo><msub><mi>r</mi><mi>A</mi></msub><mo stretchy=\"false\">⟩</mo></math></span></span><script type=\"math/mml\"><math display=\"inline\" overflow=\"scroll\"><mo stretchy=\"false\">⟨</mo><msub><mi>r</mi><mi>A</mi></msub><mo stretchy=\"false\">⟩</mo></math></script>), A-site size disorder parameter (σ<sup>2</sup>) and the associated local lattice deformation, external pressure, and electric and magnetic fields. The magneto-electronic inhomogeneity is believed to play a crucial role in the emergence of CMR. The Griffiths phase magnetic inhomogeneity possesses an undecided disposition to the emergence of CMR. Here, we report investigation on electrical and magneto-electric transport properties on a series of high entropy manga","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"41 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857889","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Simultaneous Superconducting and Topological Properties in Mg–Li Electrides at High Pressures","authors":"Dan Wang, Hongxing Song, Qidong Hao, Guangfa Yang, Hao Wang, Leilei Zhang, Ying Chen, Xiangrong Chen, Huayun Geng","doi":"10.1021/acs.jpcc.4c06309","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06309","url":null,"abstract":"Electrides as a unique class of emerging materials exhibit fascinating properties and hold important significance for understanding matter under extreme conditions, which is characterized by valence electrons localized into the interstitial space as quasi-atoms (ISQs). In this work, using crystal structure prediction and first-principles calculations, we identified seven stable phases of Mg–Li that are electrides with novel electronic properties under high pressures. Among them, MgLi₁₀ is a semiconductor with a band gap of 0.22 eV, and <i>Pm-</i>3<i>m</i> MgLi is a superconductor with a superconducting transition temperature of 22.8 K. The important role played by the localization degree of ISQs in the superconducting transition temperature of these electrides is revealed by systematic comparison of Mg–Li with other Li-rich electride superconductors. Furthermore, we proved that <i>Pm-</i>3<i>m</i> MgLi and <i>Pnma</i> MgLi also have distinct topological behavior with metallic surface states and the nonzero <i>Z</i>₂ invariant. The simultaneous coexistence of superconductivity, electronic band topology, and electride property in the same structure of <i>Pm-</i>3<i>m</i> MgLi and <i>Pnma</i> MgLi demonstrates the feasibility of realizing multiquantum phases in a single material, which will stimulate further research in these interdisciplinary fields.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"13 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849838","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spectral Signatures of Polarons and Bipolarons in P3HT: Single Chains vs π-Stacks","authors":"Mohammad Balooch Qarai, Nicholas J. Hestand, Frank C. Spano","doi":"10.1021/acs.jpcc.4c06880","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06880","url":null,"abstract":"The impact of interchain interactions on the mid-IR absorption spectrum of polarons and bipolarons in π-stacked aggregates of p-doped conjugated polymers is investigated theoretically. These systems are described using a Hamiltonian that allows for hole hopping in two dimensions, as well as the hole–hole and counterion–counterion repulsive Coulombic interactions and the attractive hole–counteranion interactions. Interchain interactions are found to dramatically increase the bipolaron binding energy as well as the singlet–triplet energy gap. They also lead to an additional near-IR peak in the bipolaron spectrum that is blue-shifted relative to the polaron P₁ band, thereby accounting for measurements on electrochemically doped P3HT. Ionized multipolaron complexes are also investigated and are shown to contribute additional red and blue-shifted spectral bands.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"256 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841884","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Insight into the Injection Rate Effects on Residual Liquid Film in Tight Sandstone Nanopore","authors":"Zhinan Liu, Xiang Wang, Guicai Zhang, Rongkai Yuan","doi":"10.1021/acs.jpcc.4c07736","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07736","url":null,"abstract":"Waterflooding in tight reservoirs is a key focus in the recent oilfield development, making it essential to accurately assess the injection rate effect in tight sandstone. This study investigates the relationship between injection rate and residual liquid film (water and oil film) thickness, as well as the underlying mechanisms, by conducting oil-driven water experiments combined with molecular dynamics simulations. The morphology of the liquid film formed under different injection rates serves as the primary focus of this research. The experimental results indicate that as the oil injection rate increases, the volume of stagnant water and bound water gradually decreases and stabilizes. Molecular dynamics simulations results reveal that the displacement process can be categorized into three stages: a rapid injection stage, a slow injection stage, and a smooth injection stage. In the oil-driven water system, the thickness of the final water film is more uniform. As the injection rate increases, the recovery rate gradually decreases. However, once the injection rate reaches a certain threshold, the rate of decline in recovery rate slows down. This study provides a theoretical foundation and reference data for selecting optimal injection rates in waterflooding operations for tight reservoirs, contributing to improved recovery rate and velocity.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"24 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"One Pot Synthesis of Cyan Emitting CdZnSSe Quantum Dots for Human Centric Lighting","authors":"Abraham J. Jordan, Zhuolei Zhang, Ellie Bennett, Leslie Guadalupe Castro, David Jingbo Han, Iva Rreza, Ayelet Teitelboim, Brian Theobald, Bereket Zekarias, Emory M. Chan, Jonathan S. Owen","doi":"10.1021/acs.jpcc.4c07446","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07446","url":null,"abstract":"A one pot synthesis of blue and green emissive CdZnSSe quantum dots (QDs) from thio- and selenoureas and Cd and Zn carboxylates is optimized using high throughput robotic optimization. A large set of spectral data (<i>N</i> = 192) is used to train machine learning models that accurately predict the photoluminescence emission wavelength (λ_max) and full-width half-maximum, and the relative photoluminescence quantum yield (PLQY) from the S:Se and Zn:Cd stoichiometries and reaction time. ZnS shells are deposited on the crude QD heterostructures using 4-<i>tert</i>-butylbenzyl mercaptan, a more reactive source of sulfide that enables shell growth below the temperature where ion diffusion in the QD can broaden its optical spectrum (≤275 °C). These optimized procedures provide gram quantities of blue-green emitting QDs (PLQY = 85–99%) in a single reaction vessel. A solid state lighting device (4260 K) that incorporates cyan emissive QDs achieved a higher luminous efficacy of 179 lm/W and melanopic daylight efficiency ratio (0.71) than existing commercial human centric lighting devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"16 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849798","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydrated Electrocatalysis: To Boost the Selectivity for the Oxygen Evolution Reaction in Seawater Electrolysis","authors":"P. Vignesh Raja, Padinjarethil Vishnu, Tanmay Kumar Panigrahi, Ravi Sankannavar, Sai Phani Vangala, Ijjada Mahesh","doi":"10.1021/acs.jpcc.4c06083","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06083","url":null,"abstract":"The increase in the production of renewable electricity offers the opportunity to transition from the usage of fossil-based hydrogen to green hydrogen. While mass production of green hydrogen by water electrolysis demands substantial freshwater resources, the abundant availability of seawater provides a promising opportunity to directly use it as an electrolyte in a water electrolyzer. However, a major challenge in seawater electrolysis is the low selectivity for oxygen evolution compared to the chlorine evolution at the anode. To address this, we proposed a strategy to boost the selectivity for oxygen evolution by hydrated electrocatalysis, in which water is itself part of the catalyst. Water molecules that are coordinately bonded to the active catalytic sites play a significant role in enhancing oxygen evolution selectivity. This approach was demonstrated with Prussian blue analogue electrocatalysts in acidified simulated seawater electrolyte using rotating ring disk electrode voltammetry. Microkinetic modeling was employed to correlate the coverage by the reactants (H₂O and Cl^–) with selectivity. Notably, the crystal water coverage on hydrated electrocatalysts emerged as the partial descriptor for the selectivity of the oxygen evolution reaction. To gain insights for coverage by crystal water and Cl^–, the thermogravimetric analysis combined with Rietveld refinement and microkinetic Tafel analysis was performed. In a nutshell, we explored the question: if the reactant molecule (H₂O) is an integral part of the catalyst, can it promote the corresponding electrochemical oxidation reaction (O₂ evolution) over its competitor (Cl₂ evolution)?","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"79 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841882","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydration Processes of the Proton-Conducting Hexagonal Perovskites Ba7In6–xYxAl2O19","authors":"Roman D. Andreev, Irina E. Animitsa","doi":"10.1021/acs.jpcc.4c06688","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06688","url":null,"abstract":"The crystal structure, TG-MS, IR, and hydration thermodynamic parameters of the inherently oxygen-deficient Ba₇In_6–<i>x</i>Y_<i>x</i>Al₂O₁₉ system have been investigated. X-ray diffraction analysis showed that the Ba₇In_6–<i>x</i>Y_<i>x</i>Al₂O₁₉ (0 ≤ <i>x</i> ≤ 0.25) are hexagonal perovskites belonging to the <i>P</i>6₃<i>/mmc</i> space group. The hydrated materials exhibited the same structure with larger cell parameters. IR spectroscopy of the hydrated specimens confirmed the existence of three types of hydroxyl groups involved in different hydrogen bonds. The dissolution of water was measured by using thermogravimetric (TG) analysis. The TG measurements showed the water uptake growth with increase of <i>x</i>. Dehydration upon heating is a three-stage process, namely, two close effects in the temperature range 200–600 °C and a small high-temperature effect near 800 °C. A defect chemical model was developed to derive hydration thermodynamic parameters based on TG data. A thermodynamic approach to the hydration process showed that the increase in the Y³⁺ content was accompanied by a decrease in the enthalpy of hydration due to the enlargement in the basicity of the phases. The strategy of introducing an isovalent dopant with a larger size and lower electronegativity turned out to be favorable in terms of increasing the proton concentration and decreasing the enthalpy of hydration.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"31 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849774","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Regulation of Bi7–xPrxTi3Fe3O21 Ferroelectrics/Relaxor Ferroelectrics","authors":"Chunyan He, Yang Li, Hongyu Guo, Zhien Wang, Yulong Bai, Shifeng Zhao","doi":"10.1021/acs.jpcc.4c06926","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06926","url":null,"abstract":"The programmable relaxor ferroelectrics are realized in continuous-component Bi_7–<i>x</i>Pr_<i>x</i>Ti₃Fe₃O₂₁ (0 ≤ <i>x</i> ≤ 1.2) films, which provide a platform for investigating the relaxor ferroelectric phase transition. The robust ferroelectric loops that degenerate into tenuous curves and the evident shifting of the dielectric peak serve as compelling evidence, upon which the scaling law of relaxor ferroelectrics is extracted by Arrot plot and Vogel–Fulcher relations. The discrepancies in size between the donor Pr³⁺ and the acceptor Bi³⁺ result in lattice distortions and cation disorder, which diminish the dimensions of the ferroelectric domains and impede long-range dipole interactions. The domain flips result in an enhanced relaxor trait as well as a decrease in the Curie temperature. Ultimately, the ferroelectric photovoltaic effect is observed, which elucidates the genesis of the photocurrent and the diagram of A-site disorder relaxor ferroelectrics.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"86 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Accurate Singlet–Triplet Excited States Energy Gap Can Be Mastered by Time-Dependent Density Functional Theory Calculations Based on a Dielectric-Screened Range-Separated Hybrid Functional","authors":"Roshan Khatri, Barry D. Dunietz","doi":"10.1021/acs.jpcc.4c04178","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c04178","url":null,"abstract":"The energy gap between the lowest singlet and lowest triplet excited states of molecular emitters is a key property affecting their thermally activated delayed fluorescence (TADF) functionality. In cases in which these states are marked by internal charge transfer, the molecular environment of the emitter significantly stabilizes these states. To address this challenging relationship, a recently developed density functional theory (DFT) framework that alleviates the fundamental orbital gap in the gas phase can be employed, offering a highly effective and predictive description of these states. These modern functionals, range-separated hybrid functionals, are based on a generalized Kohn–Sham exchange functional expression where electronic interactions are separated into long and short ranges. For representing the significant condensed phase effects, especially in the case of charge transfer states, dielectric screening can be affected by functional expression. Dielectric-screened range-separated functionals that are invoked within a polarizable continuum model were shown to properly address the orbital gap challenge in the condensed phase and consequently benchmark well in calculating triplet and charge transfer excited states. We address the excited singlet–triplet state energy gap using such a screened range-separated functional and find that the calculated gaps tend to fall within 0.1 eV of the measured energies for a widely addressed benchmark set. Here, we emphasize the success of the dielectric-screened DFT framework in calculating these important energy gaps, reproducing well the benchmark values and therefore alleviating concerns about the applicability of existing functionals. We posit that dielectric-screened calculations will bear increasing impact on the design of organic materials aiming to enhance optoelectronic applications and in particular of realized TADF efficiencies.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"11 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced Efficiency and Delayed Decay of Organic Light-Emitting Diodes by Incorporating Spacer Layer Based on Low-Triplet Energy Interfacial Exciplex","authors":"Jingyu Wang, Tingyu Pan, Danyang Zhang, Haoran Yang, Guibin Wang, Liang Zhou","doi":"10.1021/acs.jpcc.4c06784","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06784","url":null,"abstract":"Although the performance of solution-processed organic light-emitting diodes (OLEDs) has been significantly increased, blue emission remains the key problem in the technology. Since the matched host materials should possess appropriate energy levels and high carrier mobility as well as higher triplet energies, it is really difficult to design and select the matched exciplex host materials. Herein, a simple donor–spacer–acceptor (D–S–A) structure for blue phosphorescent OLEDs with FIr6 as the blue emitter is reported. This design strategy is particularly efficient, and the performances of solution-processed blue phosphorescent OLEDs with a low triplet energy interfacial exciplex as the host were successfully enhanced by manipulating excitons and carriers via incorporating a bipolar spacer layer. The optimal device realized the maximum current efficiency of 31.99 cd/A, maximum external quantum efficiency of 19.01%, and maximum brightness of 15190 cd/m². The efficiency roll-off ratio at 1000 cd/m² was significantly decreased from 45.49% (primary device) to 10.00% (optimal device) due to improved carrier balance and well confined excitons. Notably, performances of the obtained device were better than the best records of solution-processed OLEDs with FIr6 as the emitter. More excitingly, this strategy is also successful in the development of high-performance white OLEDs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"21 2 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}