Physical Chemistry Chemical Physics最新文献

Phonon-mediated superconductivity in the metal diborides XB2 under pressure

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-28 DOI: 10.1039/d5cp00342c

Zhi-Yuan Qiu, Wen-Guang Li, Zheng-Tang Liu, Qi-Jun Liu

{"title":"Phonon-mediated superconductivity in the metal diborides XB2 under pressure","authors":"Zhi-Yuan Qiu, Wen-Guang Li, Zheng-Tang Liu, Qi-Jun Liu","doi":"10.1039/d5cp00342c","DOIUrl":"https://doi.org/10.1039/d5cp00342c","url":null,"abstract":"As a promising candidate for high-temperature superconductors, the AlB2 structure has garnered significant attention. Notably, the discovery of MgB2, which is stable at zero pressure and exhibits a high Tc of 39 K, has sparked a surge in research on metal borides. Metals, acting as electron donors, play a crucial role in stabilizing the relative positions of metal and boron atoms, thereby contributing to the stabilization of the crystal structure and the enhancement of superconductivity. In this study, the Mg atom was replaced with another metal atom X (X = Li, Ca, Sc, Ti, V, Rb, Zr, Nb, Cs, Ba, Hf, Ta). The resulting 12 compounds demonstrated stability at zero or low pressure. However, none of these compounds exhibited superconductivity comparable to that of the parent MgB2. Among them, LiB2, CsB2, and RbB2 emerged as the most promising candidates for superconductors. These findings highlight the complex interplay between the density of electronic states at the Fermi level and electron–phonon coupling in determining the superconductivity of binary metal borides. The computational results provide valuable insights for future research and the design of new superconducting materials within this family of metal compounds.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"23 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723790","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}

引用次数: 0

A Redefinition of Global Conceptual Density Functional Theory Reactivity Indexes by means of the Cubic Expansions of the Energy

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-28 DOI: 10.1039/d5cp00994d

Luis C. Rincón, Wendy M. Rodríguez, Jose R. Mora, Cesar H Zambrano, Luis E. Seijas, Andrés Reyes, Fernando Javier Torres

引用次数: 0

Quantifying lattice vibrational modes and optical conductivity in mixed magnetite-maghemite nanoparticles

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-28 DOI: 10.1039/d5cp00503e

Mireia Sainz-Menchón, Inigo González de Arrieta, Telmo Echániz, Karam Nader, Maite Insausti, Aurélien Canizares, Olivier Rozenbaum, Gabriel A. López

{"title":"Quantifying lattice vibrational modes and optical conductivity in mixed magnetite-maghemite nanoparticles","authors":"Mireia Sainz-Menchón, Inigo González de Arrieta, Telmo Echániz, Karam Nader, Maite Insausti, Aurélien Canizares, Olivier Rozenbaum, Gabriel A. López","doi":"10.1039/d5cp00503e","DOIUrl":"https://doi.org/10.1039/d5cp00503e","url":null,"abstract":"Magnetite nanoparticles are an important nanomaterial with promising biomedical applications that depend crucially on their stoichiometry. Their tendency to oxidize and turn into isostructural maghemite means that discriminating between both oxides is a essential task that is difficult to achieve with conventional techniques. In this work, a novel methodology based on infrared spectroscopy is developed and tested with practically relevant magnetic nanoparticles. In contrast to Raman spectroscopy, which is prone to systematic errors and only offers a qualitative understanding of the vibrational properties, infrared spectroscopy is not only able to identify all the modes corresponding to magnetite and maghemite, but also capable of discriminating between two possible structural variants of maghemite. Additionally, the proposed approach also allows the acquisition of electrical conductivity, a property that is sensitive to the structure and stoichiometry of the particles. Together, vibrational mode modeling and conductivity quantification provide a detailed picture of the structure and properties of mixed iron oxide nanoparticles that is valuable towards an advanced characterization of magnetic nanomaterials in real biomedical applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"14 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723789","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}

引用次数: 0

Reinforcement learning-based inverse design of composite films for spacecraft smart thermal control

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-28 DOI: 10.1039/d5cp00039d

Yongxing Chen, Haining Ji, Peng Long, Bin Liu, Yi Wang, Yangyong Ou, Cong Deng, Yan Huang, Junlong Wang

{"title":"Reinforcement learning-based inverse design of composite films for spacecraft smart thermal control","authors":"Yongxing Chen, Haining Ji, Peng Long, Bin Liu, Yi Wang, Yangyong Ou, Cong Deng, Yan Huang, Junlong Wang","doi":"10.1039/d5cp00039d","DOIUrl":"https://doi.org/10.1039/d5cp00039d","url":null,"abstract":"Thermal control is crucial for the normal operation of spacecraft, as it directly affects the performance and lifespan of the payload. The thermochromic properties of VO2 give it a natural advantage in smart thermal control of spacecraft, but traditional design methods still struggle to meet the design expectations for thermal control composite films. Based on this, this paper focuses on the thermal control requirements for spacecraft and proposes the design of composite films that integrate the coordinated control of dynamic thermal emitters and solar reflectors using machine learning algorithms. Firstly, a reinforcement learning optimization framework was constructed using a transfer matrix method combined with deep Q-learning. Multiple Fabry–Pérot resonator stacked structures have been optimized for the design of dynamic thermal emitters. The results indicated that a three-resonator stacked structure achieved a wide adjustable emissivity range of 0.939 near the 10 μm wavelength band. Based on this structure, a solar reflector was further designed to achieve low absorption in the solar wavelength band. The resulting smart thermal control composite film achieved a low absorption of 0.180 in the solar wavelength band, while maintaining a high emissivity adjustable range of up to 0.806. The simulated thermal control performance in a space environment indicates that, accounting for solar absorptivity, the cooling power of the film can shift from −183.42 W m−2 to 83.13 W m−2 before and after the phase transition. Furthermore, the composite film can maintain good thermal control performance within a large range of incident angles, promoting the practical application research of smart thermal control composite films.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"72 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723791","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}

引用次数: 0

Study of Decahedral Multimetallic Nanoparticles Using Large-Angle Convergent-Beam Electron Diffraction

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-28 DOI: 10.1039/d5cp00109a

Blake K Rogers, Carlos Eduardo Rufino da Silva, Juan Pedro Palomares Báez, Jesus J. Velazquez-Salazar, José Luis Rodríguez-López, Juan Martin Montejano-Carrizales, Miguel Jose Yacaman

引用次数: 0

Effect of Back Skeleton Ligand on Ultrafast Excited-state Dynamics of Cu(I) Cyano Substituted Bipyridine Complexes

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-28 DOI: 10.1039/d4cp03464c

Guanzhi Wu, Qingxue Li, Jing-Lin Chen, Wenkai Zhang

{"title":"Effect of Back Skeleton Ligand on Ultrafast Excited-state Dynamics of Cu(I) Cyano Substituted Bipyridine Complexes","authors":"Guanzhi Wu, Qingxue Li, Jing-Lin Chen, Wenkai Zhang","doi":"10.1039/d4cp03464c","DOIUrl":"https://doi.org/10.1039/d4cp03464c","url":null,"abstract":"Cu(I) complexes have attracted a lot of research interest for their potential replacement of functional noble metal complexes. In previous researches of Cu(I) complexes’ ultrafast dynamics, most of the acceptor ligands used are symmetric and only a limited number of asymmetric ligands examples were reported. To further understanding the ultrafast excited states’ dynamics of Cu(I) complexes with asymmetric cyano-substituted bipyridine electron acceptors ligand, Cu(I) complexes with 6-cyano-2,2ʹ-bipyridine and 4,4ʹ-dimethyl-6-cyano-2,2ʹ-bipyridine ligand in dichloromethane and acetonitrile were investigated by applying femtosecond time-resolved transient absorption (TA) spectroscopy. From the TA spectra, it was found that there are two different metal-to-ligand charge transfer (MLCT) states with different nature could be populated after pseudo-Jahn-Teller distortion. Time-dependent density functional theory (TD-DFT) calculation results also support this hypothesis that in one MLCT state, electron density is donated from Cu(I) center to the cyanobipyridine ligand with electron density delocalised on the whole bipyridine ligand and in the other MLCT state is with electron density donated from Cu(I) center to the cyano-substituted pyridine fragment of the cyanobipyridine ligand. This result indicates that asymmetric electron acceptors may lead to extra excited states could be populated comparing with symmetric electron acceptors.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"90 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723794","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}

引用次数: 0

Fitting ambiguities mask deficiencies of the Debye–Hückel theory: revealing inconsistencies of the Poisson–Boltzmann framework and permittivity

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-28 DOI: 10.1039/d5cp00646e

Benjamin Janotta, Maximilian Schalenbach, Hermann Tempel, Rüdiger-A. Eichel

{"title":"Fitting ambiguities mask deficiencies of the Debye–Hückel theory: revealing inconsistencies of the Poisson–Boltzmann framework and permittivity","authors":"Benjamin Janotta, Maximilian Schalenbach, Hermann Tempel, Rüdiger-A. Eichel","doi":"10.1039/d5cp00646e","DOIUrl":"https://doi.org/10.1039/d5cp00646e","url":null,"abstract":"The more than 100-year-old Debye–Hückel theory displays the most widely used approach for modeling ionic activities in electrolytes. The Debye–Hückel theory finds widespread application, such as in equations of state and Onsager's theory for conductivities. Here, a theoretical inconsistency of the Debye–Hückel theory is discussed, which originates from the employed Poisson–Boltzmann framework that violates the statistical independence of states presumed for the Boltzmann statistics. Furthermore, the static permittivity of electrolytic solutions is discussed as not directly measurable, while common methods for its extraction from experimental data are assessed as erroneous. A sensitivity analysis of modeled activity coefficients with respect to the permittivity and ionic radii as input parameters is conducted, showing that their influences overshadow physicochemical differences of common variations of Debye–Hückel models. Eventually, this study points out that the justification of the traditional and still often used Debye–Hückel models by experimental validation is affected by fitting ambiguities that eventually impede its predictive capabilities.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"98 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723792","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}

引用次数: 0

Observation of the hemibond formation in (H2O-Arn)+ radical cation clusters by electronic spectroscopy and ion imaging technique

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-28 DOI: 10.1039/d5cp01001b

Mizuhiro Kominato, Takumi Koshiba, Fuminori Misaizu, Asuka Fujii

{"title":"Observation of the hemibond formation in (H2O-Arn)+ radical cation clusters by electronic spectroscopy and ion imaging technique","authors":"Mizuhiro Kominato, Takumi Koshiba, Fuminori Misaizu, Asuka Fujii","doi":"10.1039/d5cp01001b","DOIUrl":"https://doi.org/10.1039/d5cp01001b","url":null,"abstract":"The hemibond is a non-classical covalent bond formed by the overlap of non-bonding orbitals of a radical (cation) and a closed-shell molecule. For (H2O-Arn)+ radical cation clusters, competition between the hemibonded type and hydrogen-bonded (H-bonded) type isomers has been discussed on the basis of infrared spectroscopy and theoretical computations. It has been commonly recognized that the H-bonded type is predominant, while the coexistence of the hemibonded type remains a topic of debate. Hemibonded species are known to exhibit very strong electronic transitions in the ultraviolet and/or visible (UV-Vis) region, which are marker bands for hemibond formation. In this study, we performed electronic spectroscopy and photofragment ion imaging experiments on (H2O-Arn)+ to observe the hemibond formation between H2O+ and Ar. The observed spectra of (H2O-Arn)+ (n = 1-3) exhibit absorption in the UV and visible regions. A comparison with quantum chemical calculations suggests the coexistence of the hemibonded type in (H2O-Arn)+ (n = 1 and 2). In addition, the photofragment ion imaging experiment on (H2O-Ar)+ showed an angular distribution attributed to the absorption of the hemibonded type, providing firm experimental evidence of the coexistence of the hemibonded type.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"59 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143733971","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}

引用次数: 0

High-temperature NMR Investigation of the Structural Evolution and the Special Phase Transition in LiF-NaF-BeF2 Mixed Salt Melts

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-28 DOI: 10.1039/d5cp00378d

Jianchao Sun, Hailong Huang, Ling Han, Xiaobin Fu, Hong-Tao Liu, Yuan Qian

引用次数: 0

Analysis of the impact of protein conformational dynamics and intermolecular interactions on water flux through TIP3;1 aquaporins of Zea mays L.

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-27 DOI: 10.1039/d4cp04661g

Diego Fernando Nieto-Giraldo, José Mauricio Rodas Rodríguez, Javier Ignacio Torres-Osorio

{"title":"Analysis of the impact of protein conformational dynamics and intermolecular interactions on water flux through TIP3;1 aquaporins of Zea mays L.","authors":"Diego Fernando Nieto-Giraldo, José Mauricio Rodas Rodríguez, Javier Ignacio Torres-Osorio","doi":"10.1039/d4cp04661g","DOIUrl":"https://doi.org/10.1039/d4cp04661g","url":null,"abstract":"The discovery of aquaporins (AQPs) in 1992 had a profound impact on our understanding of the mechanisms underlying the transport of substances across cell membranes. To further understand water mobilization through AQPs, this study focuses on the characterization of water flux through the TIP3;1 aquaporins of Zea mays L. using molecular dynamics. The primary objective is to elucidate how protein–water intermolecular interactions and protein conformational dynamics impact water mobility across the cell membrane. To conduct this analysis, the three-dimensional structure of TIP3;1 was modeled using AlphaFold2, from which the complete system was constructed. This system consisted of a homotetramer of TIP3;1 immersed in a fragment of cell membrane and solvated with water molecules and ions. Subsequently, molecular dynamics simulations were conducted for 90 ns, resulting in the determination of an osmotic permeability coefficient (pf) of 0.8172 ± 0.146 × 10−14 cm3 s−1. In general, the mobility of water along the single-file water channel is influenced by the complex interplay of protein conformational dynamics and hydrogen bonding. The conformational dynamics of the protein channel modify the pore radius available for the passage of water, which affects the frequency of protein–water interactions and consequently influences the mobility of water in the channel. This study contributes to our understanding of the molecular mechanisms by which AQP activity is modulated without involving changes in protein chemical composition.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"36 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723795","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}

引用次数: 0