The Journal of Physical Chemistry C最新文献

{"title":"Application of High-Resolution 95Mo Solid State NMR Spectroscopy in Structural Studies of Complex Alkali Molybdate Crystals and Glasses","authors":"Sabyasachi Sen, Ivan Hung, Jacob M. Lovi, Zhehong Gan","doi":"10.1021/acs.jpcc.5c00614","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00614","url":null,"abstract":"The Mo–O coordination environment is probed in a series of simple and complex crystalline alkali molybdates as well as in mixed-alkali molybdate glasses using high-field (18.8 and 20.0 T) ⁹⁵Mo magic-angle-spinning (MAS) and multiple-quantum MAS (MQMAS) nuclear magnetic resonance (NMR) spectroscopy. When taken together, the ⁹⁵Mo NMR spectroscopic results indicate that somewhat contrary to the conventional wisdom the corner- and edge-shared MoO₆ octahedral sites in these alkali molybdates are characterized by higher values of the isotropic shift (δ_iso) and quadrupolar coupling constant (<i>C</i>_Q) compared to the MoO₄ tetrahedral sites. These trends are hypothesized to be related to the unusually strong distortion of MoO₆ octahedra in corner- and edge-shared configurations and the resulting increase in the paramagnetic component of the chemical shift. While the ⁹⁵Mo <i>C</i>_Q of the MoO₄ sites displays an approximately linear positive correlation with the degree of tetrahedral distortion, no such correlation is observed for the MoO₆ sites. High-resolution ⁹⁵Mo NMR spectra show the coexistence of tetrahedral and octahedral Mo–O environments in the structure of alkali molybdate glasses, with the relative fraction of the latter environment increasing with Mo content. The results presented in this study indicate that high-resolution ⁹⁵Mo NMR spectroscopy at high magnetic fields (∼20 T or higher) may prove to be a promising tool for investigating the Mo–O coordination environments in nuclear waste glasses.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"100 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143724011","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":"Long-Lived Charge-Transfer Excitons in a Graphene–PTCDI–TiOPc Trilayer Heterostructure","authors":"Ryan J. Scott, Neno Fuller, Adithya Sadanandan, Pavel Valencia-Acuna, Wai-Lun Chan, Qunfei Zhou, Hui Zhao","doi":"10.1021/acs.jpcc.5c00969","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00969","url":null,"abstract":"Excitation transfer across the interfaces between graphene, perylenetetracarboxylic diimide (PTCDI), and titanyl phthalocyanine (TiOPc) was studied by using transient absorption and photoluminescence spectroscopy. Both photoluminescence quenching and transient absorption measurements confirm the presence of a type-II interface between PTCDI and TiOPc. While the graphene/PTCDI interface is expected to exhibit type-I behavior, transient absorption measurements indicate that only electrons transfer from PTCDI to graphene, with no evidence of hole transfer. Density functional theory calculations reveal significant ground-state electron transfer from graphene to PTCDI, resulting in band bending that prevents excited holes from transferring from PTCDI to graphene. This feature is exploited in a trilayer heterostructure of graphene/PTCDI/TiOPc, where the spatial separation of photoexcited electrons and holes in graphene and TiOPc, respectively, leads to the formation of long-lived photoexcitations with a lifetime of approximately 500 ps. Furthermore, spatially resolved transient absorption measurements reveal the immobile nature of these excitations, confirming that they are charge-transfer excitons rather than free electrons and holes. These results provide valuable insights into the complex interlayer photoexcitation transfer properties and demonstrate precise control over the layer population and the recombination lifetime of photocarriers in such hybrid heterostructures.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"2 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713550","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":"Overall Water Splitting of the Direct Z-Scheme vdW Heterojunction GeC/ZrS2","authors":"Helong Yang, Hongxiang Deng, Biyi Wang, Xia Xiang, Xiaotao Zu","doi":"10.1021/acs.jpcc.5c01067","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01067","url":null,"abstract":"Direct Z-scheme heterojunctions can realize the effective space separation of electrons and holes under light radiation. Therefore, it has an obvious advantage for water splitting. In this work, we have designed and studied a new heterojunction, GeC/ZrS₂, with a direct Z-scheme band arrangement. Both monolayer GeC and monolayer ZrS₂ in the present GeC/ZrS₂ heterojunction are easily prepared. We also systematically investigated the electronic and optical properties of the GeC/ZrS₂ heterojunction. The calculated binding energy and phonon spectra show that the GeC/ZrS₂ heterojunction has good stability. The electronic structure and band arrangement show that GeC/ZrS₂ is a direct Z-scheme energy band arrangement with a suitable band gap (1.19 eV) for photocatalytic water decomposition. The GeC/ZrS₂ heterojunction shows good absorption coefficients (reaching 10⁵ cm^–1) in the visible and ultraviolet ranges. The GeC/ZrS₂ heterojunction has excellent carrier mobilities in both the armchair and zigzag directions, and the electron mobility can reach 1502.78 cm² V^–1 s^–1 in the zigzag direction, which is good for the space separation of electrons and holes under light radiation. The Gibbs free energy shows that the GeC/ZrS₂ heterojunction can achieve overall water splitting at pH = 14 and an external voltage of 3.3 eV. The solar to hydrogen (STH) production efficiency is 28.7%. Moreover, the GeC/ZrS₂ heterojunction can achieve a direct Z-scheme band arrangement, and the biaxial strain can further increase the band gap and improve the photocatalytic performance. Our results show that the heterojunction GeC/ZrS₂ has excellent potential for overall photocatalytic water splitting.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"30 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713551","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":"Correction to “Correlations of Ionic Migration and Deep-Level Traps Lead to Surface Defect Formation in Perovskite Solar Cells”","authors":"Xue Zheng, Xiao Wang, Weimin Li, Zhenghao Liu, Wenjie Ming, Huan Wang, Han Wang, Da Li, Bo Liu, Chunlei Yang","doi":"10.1021/acs.jpcc.5c01843","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01843","url":null,"abstract":"The acknowledgment is corrected as given below. The added project number is highlighted in bold. This work is primarily sponsored by National Natural Science Foundation of China (Grant No. 52003288, 61774164,22003074). The computational work is conducted at Center for Computational Science and Engineering at the Southern University of Science and Technology. We acknowledge financial support from the National Key R&amp;D Program of China (Grant No. 2018YFB1500200). This work is partially supported by the Shenzhen Science and Technology Program(JCYJ20200109114801744, JCYJ20190807161001747, and <b>JCYJ20210324101801004</b>). This article has not yet been cited by other publications.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"35 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713552","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":"Quantum Rotor Qubits in Metal Halide Perovskites","authors":"Xiao-Zhe Zhang, Hong-Juan Li, Ran-Bo Yang, Xiao-Qi Dong, Zhi-Qing Li, Zi-Wu Wang","doi":"10.1021/acs.jpcc.4c08284","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08284","url":null,"abstract":"The schemes of a single molecule for constructing quantum bits (qubits) have aroused intense interest in the field of quantum information science. Here, we propose a qubit based on the rotational motion of the organic cation in metal halide perovskites (MHPs), in which the superposition states are composed of the ground and first-excited rotational states. We study the decoherence and the damped Rabi oscillation of this qubit due to the transfer of phonon angular momentum stemming from the coupling between the rotating cation and the phonon bath. We find that the lifetime of a qubit could reach milliseconds if only considering this decoherence source, imposing the long-lifetime boundary for this type of qubit. These results not only provide a potential platform for constructing qubits in the MHPs to explore the applications in quantum information and computation but also open up avenues for studying the fundamental physics related to the transfer of phonon angular momentum.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"35 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713765","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":"Effect of Co–Mn Ordering on Defect-Induced Modulation of Complex Magnetic, Metamagnetic, Griffiths Phase, and Exchange Bias-like Behavior of Eu2CoMnO6","authors":"Abhijit Nayak, Debasmita Bala, Athira P., Kusampal Yadav, Nasiruddin Mondal, Pranab Mandal, Venimadhav Adyam, Devajyoti Mukherjee, Bheema Lingam Chittari, Krishnamurthy Jyothinagaram","doi":"10.1021/acs.jpcc.4c07914","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07914","url":null,"abstract":"The double perovskite Eu₂CoMnO₆ (ECMO), known for its complicated metamagnetic behavior, was studied in this report to examine how postannealing synthesis affects its crystal structure and magnetic and electronic behavior. The slow-cooling, Argon treatment, and quenching procedure during the sample synthesis indicated the important significance of antisite disorder (ASD) in influencing the material’s magnetic response. The magnetic study revealed diverse transitions, including two low-temperature antiferromagnetic (AFM)-like transitions at ∼51 and ∼10 K in the slow-cooled sample and vibronic ferromagnetic (FM) superexchange interactions at ∼105 K in the argon (Ar)-treated sample, while the quenched sample displayed an AFM behavior at low temperatures. The XPS analysis indicated the presence of diverse concentrations of Co and Mn in multiple valence states, specifically (2⁺, 3⁺) and (3⁺, 4⁺) respectively, across the samples subjected to different annealing processes. The Griffiths phase was particularly noticeable in the quenched sample, highlighting the role of disorder with Griffith’s disorder exponent (λ) = 0.81. The <i>M</i>(<i>H</i>) data at 2.5 K under zero-field-cooled mode revealed that the Ar-treated sample had a smooth, saturating-like loop, while the quenched sample had the hysteresis loop shifted toward the positive field axis with a reduced magnetic moment of 2.2 μ_B/f.u., and the slow-cooled sample exhibited sharp metamagnetic jumps with an unsaturated magnetic moment of 3.3 μ_B/f.u. While <i>M</i>(<i>H</i>) data recorded under a field-cooled protocol altered the position of critical fields (<i>H</i>_C) for the slow-cooled sample, the evolution of an extra magnetization jump was noticed in the case of the Ar-annealed sample, and the quenched sample showed the loop shifting completely toward the negative field axis. The loop shift and varying <i>H</i>_C values were explained in terms of an exchange bias-like spin-pinning mechanism. Additionally, DFT calculations corroborate the experimental results, revealing an increased likelihood of antisite disorders in the presence of oxygen vacancies, as well as altered behavior of Co and Mn spin states in relation to the disorders and oxygen vacancies. The effect of the disorder and oxygen vacancies on the electrical and magnetic ground states was also investigated, and the results were complemented with the experimentally observed magnetic behavior. This study demonstrates how postannealing conditions may be carefully controlled to regulate the disorder and, thus, magnetic behavior, including valence states, Griffiths phase, and metamagnetic behavior of ECMO, opening up new avenues for developing materials with desired functional properties.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"72 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713768","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":"Emergence of an Icosahedral (H2)13 Cluster inside a Pure Silica Faujasite","authors":"G. Carneiro Queiroz da Silva, J. Marcos Salazar","doi":"10.1021/acs.jpcc.4c08679","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08679","url":null,"abstract":"We report the structuration of H₂ inside the faujasite DAY, obtained by ab initio molecular dynamics simulations at 20, 40, and 77 K. Here is detailed how the environment adjusts the rotational and vibrational modes of molecular hydrogen; also, we show the process by which the hindered rotor is altered by the temperature. By loading the faujasite with H₂, the electrical field of the host structure enhances orientational intermolecular interactions of the adsorbate molecules. The structural analysis shows an organized H₂ layer at the walls of the zeolite supercages. This organization facilitates the clustering of the non-absorbed dihydrogens. The observed cluster reminds astonishingly of the icosahedral (H₂)₁₃ structure, obtained for dihydrogen at high pressures (≈10⁵ bar). In this work, we detail the physicochemical mechanisms leading to such a structured cluster.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"25 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713769","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":"Diffusion Quantum Monte Carlo Benchmarking of Magnetic Moments in MnBi2Te4","authors":"Jeonghwan Ahn, M. Chandler Bennett, Anh Pham, Guangming Wang, Panchapakesan Ganesh, Jaron T. Krogel","doi":"10.1021/acs.jpcc.5c00051","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00051","url":null,"abstract":"The intrinsically antiferromagnetic topological insulator, MnBi₂Te₄ (MBT), has garnered significant attention recently due to its potential to host numerous exotic topological quantum states. Unfortunately, their consistent realization has been hindered by intrinsic antisite defects among the Mn and Bi sublattices. In this work, we establish Mn magnetization of pristine MBT through high level diffusion Monte Carlo calculations, which can serve as a precise starting point for various models to estimate antisite defect concentrations in actual MBT samples. The benchmark quality of DMC calculations is further identified from out model estimating antisite defect concentrations, which combines the benchmarked Mn magnetization with data from magnetic susceptibility and intermediate field magnetization measurements. This reproduces well Bi_Mn and Mn_Bi concentrations measured in the experiments. We anticipate these theoretically based magnetic purity measures may be used as minimization targets in cycles of refinement to synthesize MBT with low antisite defect concentrations and more reproducible topological properties.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"11 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713591","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":"Electron–Hole Recombination Is Suppressed by Breaking the Ring Planarity in Porphyrin Nanorings: Density Functional Atomistic Simulation","authors":"Subhajit Dey, Shrabanti Mondal, Md Habib, Ritabrata Sarkar, Sougata Pal","doi":"10.1021/acs.jpcc.5c00145","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00145","url":null,"abstract":"Porphyrin nanorings get enormous attention as potential photovoltaic materials due to their unique and tunable optoelectronic properties. Distribution of charge in porphyrin nanorings can alter the photovoltaic performance. We investigate the photodynamics of two porphyrin nanorings, i.e., fused and meso nanorings, to observe the role of charge delocalization on carrier relaxation dynamics. Employing nonadiabatic molecular dynamics within the framework of the density functional tight binding theory, we demonstrate that the meso nanoring exhibits six times longer exciton lifetime compared to the fused nanoring. Charges are more localized at the band edge states of the meso nanoring compared to fused nanoring and reduce the orbital overlap between electron and hole wave functions. As a result, localization of the charge weakens the nonadiabatic coupling, resulting in delayed electron–hole (e−h) recombination. Participation of low-frequency electron-vibrational modes and rapid decoherence at the energy gap further extends the exciton lifetime. Additional β conjunctions between the porphyrin dimer in the fused nanoring facilitate the charge delocalization throughout the nanoring because fusions between the porphyrin dimer hold the circular planarity of the nanoring. Quick charge delocalization creates a strong orbital overlap between the ground and the excited states, resulting in quick charge recombination. Further, the simulated exciton binding energy and charge transition rate support our results. We demonstrate that e−h recombination is dependent on the planarity of the porphyrin nanoring. Our simulations give light on the effect of charge localization on the carrier relaxation dynamics by tuning the geometry of the porphyrin nanoring and provide valuable guidance to design high-performance porphyrin and organic conjugated system-based optoelectronic appliances.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"21 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713771","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":"Prediction of High-Temperature Superconductivity in Cubic Ternary Hydride M3XH8 at Ambient Pressure","authors":"Bin Li, Yuxiang Fan, Junjie Zhai, Zhisi Cao, Cong Zhu, Jie Cheng, Shengli Liu, Zhixiang Shi","doi":"10.1021/acs.jpcc.5c00513","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00513","url":null,"abstract":"We present a systematic first-principles study of cubic <i>M</i>₃<i>X</i>H₈ compounds, where <i>M</i> = Li, Na, Mg, Al, K, Ca, Ga, Rb, Sr, and In and <i>X</i> represents 3d, 4d, and 5d transition metals. Our high-throughput computational screening at ambient pressure, we identify 29 dynamically stable compounds out of the 390 possible combinations. Among these, Mg₃OsH₈, Ca₃FeH₈, Al₃NbH₈, and Al₃ScH₈ attract our attention. Particularly, Mg₃OsH₈ is predicted to have remarkably high superconducting transition temperatures (<i>T</i>_c) of ∼73 K at ambient pressure. Our analysis reveals intricate relationships between crystal symmetry, electronic band structure, and superconductivity in this hydrogen-based system. We explore the role of hydrogen in mediating strong electron–phonon coupling and its impact on the superconducting properties. Furthermore, we investigate the potential Fermi surface features in the electronic structure and their correlation with superconductivity. The possible experimental synthesizability of the compounds is demonstrated by comparing their decomposition enthalpies. This work raises the prediction of ternary superconducting hydride templates, highlighting promising high-<i>T</i>_c compounds of the <i>M</i>₃<i>X</i>H₈ architecture at ambient pressure.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"183 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713774","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}