Physical Chemistry Chemical Physics最新文献

{"title":"Superconducting VF with Unusual Delocalized Electrons under High Pressure","authors":"Jianyan Lin, Siyu Liu, Yuan Yuan, Guangmin Yang, Chunyu Liu","doi":"10.1039/d5cp02282g","DOIUrl":"https://doi.org/10.1039/d5cp02282g","url":null,"abstract":"Superconductivity has been commonly found in vanadium (V) compounds, such as V-H, V-O, and V-N compounds, but with the exception of fluorides to date. Therefore, the study of V-F system for the superconductivity has drawn much attention. Here, we have systematically investigated the V-F compounds under high pressures by using first-principles swarm-intelligence structural search calculations. We found two new stoichiometries of VF and VF<small>₂</small> to become stable under high pressure. Unlike the known V-F compounds, VF and VF<small>₂</small> exhibit additional V-V interactions. Specially, there are delocalized electrons in the predicted VF structure, which gives rise to its conductivity. We further discussed the superconductive characteristics of VF by Bardeen-Cooper-Schrieffer (BCS) theory. The <em>T</em><small>_c</small> value of the predicted <em>C</em>2/<em>m</em> VF is 0.85 K. The low-frequency phonon modes of VF play a predominant role in superconductivity. In addition, we proposed the high-pressure phases of VF<small>₃</small>, VF<small>₄</small> and VF<small>₅</small> and built the V-F high-pressure phase diagram. Our work provides useful information for deeply understanding the physical and chemical properties of V-F compounds under high pressure.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"24 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319569","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":"Nonlinear optical spectroscopy of new squaraine derivatives with high potential for multidisciplinary applications.","authors":"George V Klishevich,Volodymyr O Hryn,Anton O Kostetskyi,Iaroslav B Kuziv,Igor Ya Dubey,Yuri P Piryatinski,Nataliia V Bashmakova,Andriy M Dmytruk,Viktor M Kadan,Ivan V Blonskyi,Mykhailo V Bondar","doi":"10.1039/d5cp00144g","DOIUrl":"https://doi.org/10.1039/d5cp00144g","url":null,"abstract":"New symmetrical anilinosquaraine derivatives with four hydroxyl groups in the molecular core, namely, 2,4-bis[4-[4-(3,5-didecoxyphenoxy)butyl-methyl-amino]-2,6-dihydroxy-phenyl]squaraine (1) and 2,4-bis[4-[6-(3,5-didecoxyphenoxy)hexyl-methyl-amino]-2,6-dihydroxy-phenyl]squaraine (2), were synthesized. Both compounds were found to exhibit manifold linear spectroscopic and nonlinear optical properties with high potential for a number of important multidisciplinary applications. Linear photophysical and photochemical properties of 1 and 2 were assessed in liquid solvents of different polarities at room temperature, including steady-state absorption, emission, and excitation anisotropy spectra, along with fluorescence quantum yields and lifetimes. The fast intramolecular relaxation processes in 1 and 2 were analyzed using femtosecond transient absorption pump-probe spectroscopy, and unusually strong optical amplification (gain) was observed in their narrow fluorescence contours without any evidence of solvent reorganization phenomena. The degenerate two-photon absorption (2PA) spectra of 1 and 2 were measured in a broad spectral range, and a maximum 2PA cross-section of ≈2000 GM was observed. The effect of the superluminescence of 1 and 2 was observed under femtosecond pumping, which extended their potential for photonic applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"37 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144311505","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":"Low energy pathways lead to self-healing defects in CsPbBr3","authors":"Kumar Purshottam Miskin, Yi Cao, Madaline Marland, Farhan Shaikh, David T. Moore, John Marohn, Paulette Clancy","doi":"10.1039/d5cp01641j","DOIUrl":"https://doi.org/10.1039/d5cp01641j","url":null,"abstract":"Self-regulation of free charge carriers in perovskites via Schottky defect formation has been posited as the origin of the well-known defect-tolerance of metal halide perovskite materials. Understanding the mechanisms of self-regulation promises to lead to the fabrication of better performing solar cell materials with higher efficiencies. We investigate many such mechanisms here for CsPbBr<small>₃</small>, a popular representative of a more commercially viable all-inorganic metal halide perovskite. We investigate different atomic-level mechanisms and pathways of the diffusion and recombination of neutral and charged interstitials and vacancies (Schottky pairs) in CsPbBr<small>₃</small>. We use Nudged Elastic Band calculations and ab initio-derived pseudopotentials within Quantum ESPRESSO to determine energies of formation and migration and hence the activation energies for these defects. While halide vacancies are known to exhibit low formation energies, the migration of interstitials is less studied. Our calculations uncover interstitial defect pathways capable of producing an activation energy at, or below, the single experimental value of 0.53~eV observed for the slow, temperature-dependent recovery of light-induced conductivity in bulk CsPbBr<small>₃</small>. Our work reveals the existence of a low-energy diffusion pathway involving a concerted ``domino effect'' of interstitials, with the net result that interstitials can diffuse more readily over longer distances than expected. This observation suggests that defect self-healing can be promoted if the ``domino effect'' strategy can be engaged.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"40 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319572","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":"Harnessing electrochemical CO₂ reduction and assisted water electrolysis <i>via</i> constrained thermodynamic modeling.","authors":"Jinuk Choi, Hyojung Lim, Subramani Surendran, Seonghyeon Park, Junho Shim, Gyoung Hwa Jeong, Uk Sim","doi":"10.1039/d5cp01408e","DOIUrl":"https://doi.org/10.1039/d5cp01408e","url":null,"abstract":"<p><p>Electrochemical CO₂ reduction reaction (CO₂RR) and assisted water electrolysis (AWE) using organic compounds offer promising pathways for sustainable energy conversion. However, the thermodynamic feasibility and efficiency of these processes are strongly influenced by CO₂ phase transitions (both gaseous and aqueous) and operating conditions, such as temperature and pH. This study systematically examines the thermodynamic behavior of CO₂RR and AWE by calculating Gibbs free energy (Δ<i>G</i>), enthalpy (Δ<i>H</i>), and theoretical potentials (<i>E</i>_TN and <i>E</i>_RE) over a broad temperature range (0-1000 °C) and varying pH conditions. Pourbaix diagrams for key CO₂-derived products, including CO, hydrocarbons, organic acids, and alcohols, are constructed to assess their stability across different electrochemical environments. The analysis reveals that in aqueous-phase CO₂ systems, equilibrium potentials shift due to the effects of CO₂ speciation. In alkaline conditions, dissolved CO₂ undergoes sequential conversion into HCO₃^- and CO₃^2-, resulting in increased overpotentials in CO₂RR. Conversely, gaseous CO₂ maintains a stable equilibrium potential, mitigating pH-induced fluctuations that could hinder reaction selectivity and efficiency. In AWE, the phase transition during reaction conditions lowers oxidation potentials, resulting in enhanced energy efficiency. The calculated <i>V</i>_TN and <i>V</i>_RE values demonstrate that organic oxidation reactions in AWE require substantially lower energy inputs than conventional oxygen evolution reactions, providing a thermodynamic advantage for energy-efficient hydrogen production. This study establishes a comprehensive thermodynamic framework for CO₂ electrochemical conversion, integrating Pourbaix diagrams and temperature-dependent electrochemical modeling to optimize reaction conditions and energy efficiency. These insights contribute to the rational design of electrocatalytic systems and the development of scalable CO₂ conversion technologies for industrial applications.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144323862","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":"A combined DFT calculation and experimental study of the mechanism of the SCR of NOx by NH3 over Fe-doped CoMn2O4.","authors":"Yulong Deng,Jiacheng Zheng,Wenting Chen,Xu Wang,Chengliao Deng,Xiaoming Cai,Jinming Cai,Honglin Tan","doi":"10.1039/d5cp01422k","DOIUrl":"https://doi.org/10.1039/d5cp01422k","url":null,"abstract":"NH3 selective catalytic reduction (SCR) is a promising method for NOx removal, but its low-temperature effectiveness and narrow operating window limit industrial use. This study demonstrates, through DFT calculations and experimental validation, that Fe-doped CoMn2O4 (CoFe0.1Mn1.9O4) catalysts can effectively enhance catalytic activity. Through the in-depth study of NH3-SCR, it was found that the NH3 adsorption on the catalyst surface might be significantly enhanced by the doping of Fe (Eads = -1.29 eV → -1.42 eV), and it was also further demonstrated that the NH3 had a better adsorption energy on the surface of the CoFe0.1Mn1.9O4 catalyst through the electron difference density (EDD) and partial density of states (PDOS). In addition to this, the CoFe0.1Mn1.9O4 catalyst not only reduces the first step of the dehydrogenation reaction of NH3 (Eα = 0.86 eV → 0.83 eV), but also lowers the energy barrier of the NH3-SCR (Eα = 1.11 eV → 0.86 eV). All these calculations demonstrate that Fe doping has the potential to significantly enhance catalytic performance. CoMn2O4 and Fe-doped CoMn2O4 (CoFe0.02Mn1.98O4) catalysts were synthesized using sol-gel and impregnation techniques, respectively. Through characterization and performance testing, CoFe0.02Mn1.98O4 is found to exhibit a more efficient NOx conversion (87% at 250 °C), and its N2 selectivity is also slightly improved (64%), which matches with the calculation results. In this study, a method to improve the denitrification efficiency of CoMn2O4 spinel catalysts was proposed, which provides a new idea for the development of CoMn2O4 catalysts.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"70 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144311609","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":"Component-wise AO Basis Reduction: Norm Loss, Negative Contribution Normalization, and Functional Implications","authors":"Mindaugas Macernis","doi":"10.1039/d5cp01681a","DOIUrl":"https://doi.org/10.1039/d5cp01681a","url":null,"abstract":"Atomic orbital (AO) normalization is a foundational assumption in electronic structure theory, yet in practice, the norm of contracted basis functions can deviate from unity due to internal reduction and transformation mechanisms applied by quantum chemistry packages. This work presents a systematic framework for analyzing the physical and numerical consequences of primitive basis function elimination and AO-level norm inconsistency. The implemented methodology quantifies norm loss, separates constructive and destructive contributions, and enables precise renormalization by retaining both positive and negative terms within AO representations. Using two representative systems—a Raman-active carotenoid (lycopene) and a phosphorus dimer with through-space J(P–P) coupling—sensitivity to AO normalization was evaluated. While vibrational frequencies remained stable across normalization schemes, Raman intensities and J-coupling constants showed non-negligible shifts: up to 6 Hz for phosphorus and over 50 units in Raman activity. The results demonstrate that AO normalization is not merely a numerical refinement, but a physically impactful step with implications for precision spectroscopy and quantum computing applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"138 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305476","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":"A Molecular Dynamics Study of Enhanced CO2 Separation via Boron Nitride Nanotubes Embedded in a Silicon Nitride Membrane","authors":"Winarto Winarto, Lilis Yuliati, Khairul Anam, Paul E. Brumby, Kenji Yasuoka","doi":"10.1039/d5cp01337b","DOIUrl":"https://doi.org/10.1039/d5cp01337b","url":null,"abstract":"In this work, we performed molecular dynamics (MD) simulations to investigate CO2 capture from flue gases with boron nitride nanotubes (BNNTs) and BNNTs embedded inside a silicon nitride (Si3N4) membrane. The CO2 molecules preferentially fill and occupy the BNNTs over N2 molecules. The high selectivity of BNNTs to capture CO2 rather than N2 results in a large separation effect. It was found that the CO2 molecules within the BNNTs form an ordered solid structure. Further to this, we investigated how the separation performance may be enhanced by placing BNNTs inside a silicon nitride (Si3N4) membrane. The presence of the Si3N4 membrane was found to alter the solid CO2 structures. This change is attributed to the resulting non-uniform electric field inside the BNNT. The altered electrostatic and the van der Waals interaction experienced by CO2 due to the presence of the the Si3N4 membrane leads to an enhancement of the previously mentioned separation effect. This work demonstrates the great potential for BNNTs, in particular those embedded in Si3N4 membranes, for use in carbon capture applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"23 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305477","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":"Origins of crystallisation-induced dual emission of terephthalic and isophthalic acid crystals","authors":"Ljiljana Stojanovic, Michael Dommett, Rachel Crespo-Otero","doi":"10.1039/d5cp00603a","DOIUrl":"https://doi.org/10.1039/d5cp00603a","url":null,"abstract":"Metal-free organic crystals with room-temperature phosphorescence (RTP) present an innovative alternative to conventional inorganic materials for optoelectronic applications and sensing. Recently, substantial attention has been directed towards the design of new phosphorescent crystals through crystal engineering and functionalisation. In this paper, we investigate the excited-state deactivation mechanisms of two simple organic molecules: terephthalic acid (TPA) and isophthalic acid (IPA) using embedding models based on multiconfigurational MS-CASPT2 calculations. These molecules exhibit prompt and delayed fluorescence and RTP in the solid state. We explore intramolecular internal conversion pathways using high-level quantum chemistry methods in both solution and crystalline phases. We analyse deactivation mechanisms involving singlet and triplet states, quantifying direct and reverse intersystem crossing rates from the lowest triplet states, as well as fluorescence and phosphorescence rates. Additionally, our study examines singlet exciton transport in single crystals of TPA and IPA. Our findings clarify the mechanisms underlying the prompt and delayed fluorescence and RTP of crystalline TPA and IPA, revealing distinct differences in their deactivation processes. Notably, we explain the enhanced fluorescence and phosphorescence in IPA compared to TPA, emphasising how the positioning of the carboxylic group influences electronic delocalisation in excited states, (de)stabilising delocalised ππ* states along the reaction coordinate, thereby significantly impacting deactivation mechanisms.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"37 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305473","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":"Dual-Interface Engineered SnO₂/Sn₄P₃@C Heterojunctions: Built-In Electric Field Driven Fast Kinetics for Highly Reversible Lithium Storage","authors":"Zhiqiang Huang, Zhilong Wu, Wenyi Miao, Zhongfen Yu, Hai Jia, Quanlin Chen, Xiao-Hui Huang, Zhiya Lin, shaoming Ying","doi":"10.1039/d5cp01495f","DOIUrl":"https://doi.org/10.1039/d5cp01495f","url":null,"abstract":"The practical application of SnO₂ anodes in lithium-ion batteries is fundamentally constrained by cascading challenges of structural degradation and kinetic limitations. We demonstrate a dual-interface engineering strategy through precisely controlled gas-phase phosphorization, constructing SnO₂/Sn₄P₃ heterojunctions tightly encapsulated within hierarchical carbon frameworks (SnO₂/Sn₄P₃@C, SOPC). The SnO₂/Sn₄P₃ heterojunction generates a built-in electric field, reducing charge transfer resistance and activation energy (UPS work function: 2.91 eV) and guides LiF-rich SEI formation, while the dual-carbon confinement buffers mechanical strain and ensures the structural stability with long-term cycling at high current density. These features enable hybrid storage kinetics with capacitive dominance at high rates and stable Faradaic reactions at low currents. The SOPC anode achieves exceptional cyclability with capacities of 954.8 mAh g⁻¹ after 600 cycles at 1 A g⁻¹ and 118.9 mAh g⁻¹ after 3000 cycles at 20 A g⁻¹. Full cells paired with LiFePO₄ demonstrate practical viability. This work establishes a universal interfacial engineering strategy for high-performance alloying/conversion anodes, bridging atomic-scale electronic modulation to scalable battery systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"11 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305475","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":"Enhancement the cycling stability of the nickel-rich cathode material LiNi0.9Co0.01Mn0.09O2 by Nb5+ doping","authors":"Jiatai Wang, Chao Fan, Yuanyuan Li, Yan Tan, Xuchao Zhang, Jiting Li, Hongyun Liu, Xiaohong Ma, Changjuan Deng, Jian Li","doi":"10.1039/d5cp01591j","DOIUrl":"https://doi.org/10.1039/d5cp01591j","url":null,"abstract":"LiNixCoyMn1-x-yO2 cathode materials have long been recognized as one of the most promising candidates for lithium-ion batteries. In order to increase production capacity and reduce costs, NCM cathode materials are currently developing in the direction of high nickel and low cobalt. However, these cathodes face serious challenges, such as structural instability, capacity fade, and poor rate capability. Despite extensive research, problenms of structural degradation and capacity loss under high-voltage conditions remain unresolved. In this work, we successfully prepared Nb5+-doped LiNi0.9Co0.01Mn0.09O2 cathodes by incorporating Nb2O5 into the Ni0.9Co0.01Mn0.09(OH)2 precursor powders. The Nb5+ doping not only expands the spacing of lithium layers, facilitating the diffusion of lithium ions, but also forms Nb-O bonds, enhancing the structural stability and improving the cycle performance. Electrochemical tests indicate that at a doping ratio of 1%, the first discharge specific capacity of the modified sample is 178.55 mAh/g at 1.0 C, with a capacity retention ratio of 92.69% after 100 cycles. Furthermore, the initial discharge specific capacity of the NCM-1.0Nb sample is up to 215.58 mAh/g at a high voltage of 2.5–4.5 V, and after 100 cycles, it is 188.73 mAh/g, with a cycle retention rate of 87.54%. The electrochemical cycling performance of NCM is significantly improved after doping Nb5+. Therefore, appropriate Nb5+ doping is a convenient and effective modification approach to obtain nickel-rich cathodes with excellent performance.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"5 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305472","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}