Chemphyschem最新文献

{"title":"<ArticleTitle xmlns:ns0=\"http://www.w3.org/1998/Math/MathML\">Local Structure and Dynamics in Solvent-Free Molten Salt <ns0:math> <ns0:semantics> <ns0:mrow> <ns0:msup><ns0:mrow><ns0:mi>Ca</ns0:mi></ns0:mrow> <ns0:mrow><ns0:mn>2</ns0:mn> <ns0:mo>+</ns0:mo></ns0:mrow> </ns0:msup> </ns0:mrow> <ns0:annotation>$left(text{Ca}right)^{2 &#x00026;amp;amp;amp;amp;amp;amp;plus;}$</ns0:annotation></ns0:semantics> </ns0:math> -Electrolytes.","authors":"Carolina Cruz, Patrik Johansson","doi":"10.1002/cphc.202500090","DOIUrl":"10.1002/cphc.202500090","url":null,"abstract":"<p><p>Calcium batteries (CaBs) fundamentally offer a promise of sustainable high energy density storage. However, the development of functional CaB electrolytes remains a key challenge. Here, molecular simulations are used to investigate structural and dynamic properties of solvent-free molten salt electrolytes (MSEs) containing <math> <semantics> <mrow> <msup><mrow><mtext>Ca</mtext></mrow> <mrow><mn>2</mn> <mo>+</mo></mrow> </msup> </mrow> <annotation>$left(text{Ca}right)^{2 &#x00026;amp;amp;amp;amp;amp;amp;plus;}$</annotation></semantics> </math> and alkali cations ( <math> <semantics> <mrow> <msup><mrow><mtext>Li</mtext></mrow> <mo>+</mo></msup> </mrow> <annotation>$left(text{Li}right)^{&#x00026;amp;amp;amp;amp;amp;amp;plus;}$</annotation></semantics> </math> , <math> <semantics> <mrow> <msup><mrow><mtext>Na</mtext></mrow> <mo>+</mo></msup> </mrow> <annotation>$left(text{Na}right)^{&#x00026;amp;amp;amp;amp;amp;amp;plus;}$</annotation></semantics> </math> , <math> <semantics> <mrow><msup><mi>K</mi> <mo>+</mo></msup> </mrow> <annotation>$left(text{K}right)^{&#x00026;amp;amp;amp;amp;amp;amp;plus;}$</annotation></semantics> </math> ), paired with either FSI or TFSI anions. Two equimolar MSEs, [Li, Na, K, Ca]FSI and [Li, Na, K, Ca] TFSI, are examined across a range of temperatures to better understand cation-anion interactions, coordination and local structure, and ion mobility, in particular with respect to <math> <semantics> <mrow> <msup><mrow><mtext>Ca</mtext></mrow> <mrow><mn>2</mn> <mo>+</mo></mrow> </msup> </mrow> <annotation>$left(text{Ca}right)^{2 &#x00026;amp;amp;amp;amp;amp;amp;plus;}$</annotation></semantics> </math> . The interplay between cation charge density, anion structure, and thermal effects provides valuable insights into the MSEs' macroscopic behavior. These insights inform the design of advanced electrolytes that enhance <math> <semantics> <mrow> <msup><mrow><mtext>Ca</mtext></mrow> <mrow><mn>2</mn> <mo>+</mo></mrow> </msup> </mrow> <annotation>$left(text{Ca}right)^{2 &#x00026;amp;amp;amp;amp;amp;amp;plus;}$</annotation></semantics> </math> mobility, supporting the development of next-generation CaBs.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500090"},"PeriodicalIF":2.3,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144157008","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":"Photodetachment Dynamics and Structural Flexibility of Undercoordinated Iridium Halides IrCl_n ^- (n = 3-5): An Experimental and Theoretical Investigation.","authors":"Peng Tang, Jian Zhang, Xueying Li, Fan Yang, Zhubin Hu, Haitao Sun, Xue-Bin Wang, Zhenrong Sun, Yan Yang","doi":"10.1002/cphc.202500170","DOIUrl":"10.1002/cphc.202500170","url":null,"abstract":"<p><p>Three undercoordinated iridium chloride anions, IrCl_n ^- (n = 3-5), and their neutral counterparts were investigated by cryogenic anion photoelectron spectroscopy and theoretical calculations. Photodetachment of IrCl_n ^- leads to the formation of the corresponding neutral complex, i.e., a triplet ground state for n = 3, a quartet for n = 4, and close-lying singlet and triplet for n = 5. The vertical detachment energies are determined to be 3.89, 4.98, and 5.14 eV for n = 3, 4, and 5, respectively, revealing superhalogen anion properties with increasing electron detachment energies as chloride ligands added. The IrCl₃ ^- spectrum features an extremely broad, lowest electron binding energy band, attributed to resonant autodetachment with prominent non-Franck-Condon profiles. In IrCl₅ ^-, detachment prompts a d-orbital rearrangement that drives a structural transformation from a twisted square-based pyramidal to a trigonal-bipyramidal geometry in the singlet state. These findings provide insights into the electronic and structural adaptability of iridium halides, advancing our understanding of ligand exchange reactions and dissociative stability in transition metal complexes.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500170"},"PeriodicalIF":2.3,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144141487","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":"Molecular Hydrogen as a Proton Donor in HH···F Hydrogen Bonds-BF₄ ^-···(H₂)_n Clusters.","authors":"Sławomir J Grabowski","doi":"10.1002/cphc.202500243","DOIUrl":"10.1002/cphc.202500243","url":null,"abstract":"<p><p>The MP2/6-311++G(d,p) calculations are performed to analyze geometric, energetic, and topological parameters of BF₄ ^-···(H₂)_n clusters (n up to 8). These analyses are supported by the Natural Bond Orbitals method and the Quantum Theory in Atoms in Molecules approach. The BF₄ ^- anion acts as the Lewis base since its whole molecular surface is characterized by the negative electrostatic potential. The hydrogen molecules in clusters are considered to play the role of Lewis acid ligands. These ligands are located linearly in directions being the elongation of BF bonds if the number of H₂ molecules in the cluster does not exceed 4. For the greater clusters (n ≥ 5), all H₂ molecules tend to form linear HH···F arrangements, or nearly so. However, the BF···H angles are sometimes far from linearity. The HH···F interactions may be classified as hydrogen bonds; the analysis of such interactions is also performed.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500243"},"PeriodicalIF":2.3,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144141486","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":"The Dark State, Vibronic Coupling, and Viscosity Sensing of Methoxylated Benzoyl Coumarins.","authors":"Thanh Chung Pham, Dung Ngoc Tran, Thong Van Pham, Van Trang Nguyen, Dai Lam Tran, Minh Tho Nguyen","doi":"10.1002/cphc.202500182","DOIUrl":"10.1002/cphc.202500182","url":null,"abstract":"<p><p>The 8/6-methoxylated 3-benzoyl coumarins (BC8 and BC6) are synthesized and demonstrated potential as a viscosity-sensitive fluorescent probe. To date, the mechanism of viscosity sensing has predominantly been attributed to a twisted intramolecular charge transfer effect. However, the observed fluorescence quenching is better ascribed to the presence of a dark charge transfer (¹CT) state. Fluorescence enhancement in high-viscosity media is driven by an emissive hybridized local and charge-transfer (¹HLCT) state and the suppression of the ¹HLCT → ¹CT transition and configuration conversion. Furthermore, vibronic fluorescence emission spectra at 77 K are computed using an intense adiabatic Hessian model and Voigt line shape functions to probe the contributions of Franck-Condon/Herzberg-Teller effects. The fluorescence emission and internal conversion rate at both 298 and 77 K are also theoretically determined, enabling the calculation of a fluorescence quantum yield that agrees well with experimental findings and further reconfirming the presence of ¹CT configuration. Thus, this study not only advances understanding of the dark ¹CT state of methoxylated benzoyl coumarins but also provides computational protocols for modeling ¹HLCT → ¹CT transition and vibronic emission spectra. Additionally, it offers a new molecular design and mechanism for the development of viscosity-sensitive fluorophores.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500182"},"PeriodicalIF":2.3,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144149475","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":"Porphyrin-Peptide Conjugates: Functional Self-Assembled Nanomaterials for Biomedical and Energy Conversion Applications.","authors":"Sowbhick Patra, Rakesh Gowdihalli Nagaraj, Sourav Moyra, Goutam Ghosh","doi":"10.1002/cphc.202500150","DOIUrl":"10.1002/cphc.202500150","url":null,"abstract":"<p><p>Porphyrin-peptide conjugates have emerged as promising self-assembling nanomaterials, combining the structural versatility of peptides with the exceptional optical and electronic properties of porphyrins. The extended π-conjugation of porphyrins enables strong π-π interactions, facilitating the formation of well-organized and tunable nanostructures. When conjugated with peptides, these hybrid systems exhibit enhanced biocompatibility, stimuli-responsiveness, and functional versatility, making them ideal for biomedical and energy-related applications. Their ability to self-assemble under controlled conditions allows for precise tuning of properties through pH, temperature, light, and sonication. These peptide-porphyrin conjugates have demonstrated significant potential in photodynamic therapy, photothermal therapy, drug delivery, tumor imaging, and artificial light harvesting. This review highlights the design, synthesis, self-assembly mechanisms, and diverse applications of porphyrin-peptide nanomaterials, underscoring their importance in next-generation functional materials.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500150"},"PeriodicalIF":2.3,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144131816","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":"Front Cover: Adsorption of CO on α-Al2O3(0001): A Combined Experimental and Computational Study (ChemPhysChem 10/2025)","authors":"Siddhi Gojare,&nbsp;Shuang Chen,&nbsp;Jiachen Chen,&nbsp;Zairan Yu,&nbsp;Juana Vázquez Quesada,&nbsp;Philipp N. Pleßow,&nbsp;Karin Fink,&nbsp;Yuemin Wang","doi":"10.1002/cphc.202581001","DOIUrl":"https://doi.org/10.1002/cphc.202581001","url":null,"abstract":"<p><b>The Front Cover</b> illustrates a systematic investigation of the surface structure of α-Al₂O₃(0001) by employing a multitechnique approach that combines experiment (polarization-resolved IRRAS) and theory (periodic DFT calculations and embedded quantum cluster computations). Comprehensive results obtained with CO as a probe molecule provide direct evidence of partial hydroxylation of the α-Al₂O₃(0001) surface. More information can be found in the Research Article by P. N. Pleßow, K. Fink, Y. Wang and co-workers (DOI: 10.1002/cphc.202401134).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202581001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144100529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Strategies and Challenges of Utilizing Cation Effects in Membrane Electrode Assemblies for CO₂ Reduction.","authors":"Yanhui Sun, Xuemei Du, Honghao Fan, Jinhua Ye, Lequan Liu","doi":"10.1002/cphc.202500346","DOIUrl":"10.1002/cphc.202500346","url":null,"abstract":"<p><p>Electrocatalytic CO₂ reduction in membrane electrode assembly (MEA) systems is a promising technology, enabling direct CO₂ transport to the catalyst layers and reducing ohmic resistance. While electrolyte cations are demonstrated to effectively enhance the rate and the selectivity of electrochemical reduction of CO₂, their implementation in electrolyte-free MEA electrolyzers faces significant challenges. This concept review examines key strategies for utilizing cations in MEA configurations, categorizing them into three methods: 1) incorporation of alkali metal cations into catalyst layers, 2) integration of organic cations into the cathode, and 3) mitigation of salt precipitation on the gas diffusion layers. By summarizing the challenges and proposed strategies, this review aims to provide guidance for the development of more efficient cation utilization approaches and future research in MEA-based CO₂ reduction systems.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500346"},"PeriodicalIF":2.3,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144109951","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":"Threshold Photoelectron Spectroscopy of Monosulfur Monofluoride.","authors":"Ugo Jacovella, Bérenger Gans, Myriam Drissi, Hai L Le, Mengxu Jiang, Séverine Boyé-Péronne, Gustavo A Garcia, Jean-Christophe Loison","doi":"10.1002/cphc.202500211","DOIUrl":"10.1002/cphc.202500211","url":null,"abstract":"<p><p>The study employs threshold photoelectron spectroscopy (TPES) using vacuum ultraviolet synchrotron radiation to refine spectroscopic constants and fundamental energies of monosulfur monofluoride (SF). High-precision adiabatic ionization energy (AIE) measurements are achieved that could serve as benchmarks for future calculation of heat of formation of SF and its ionized form, SF⁺. Experimental methods utilized include a microwave discharge reactor coupled with synchrotron-based spectroscopy, providing TPES and photoion yield spectra of SF. Analysis supported by ab initio calculations enables the determination of key spectroscopic parameters, including vibrational constants and ionization thresholds. The resulting AIE of 10.195(5) eV is the most accurate value to date, enhancing the reliability of thermochemical databases.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500211"},"PeriodicalIF":2.3,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144101582","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":"Cover Feature: Overcoming Challenges in Density Functional Theory-Based Calculations of Hyperfine Coupling Constants for Heavy Heteroatom Radicals (ChemPhysChem 10/2025)","authors":"Maciej Witwicki","doi":"10.1002/cphc.202581002","DOIUrl":"https://doi.org/10.1002/cphc.202581002","url":null,"abstract":"<p><b>The Cover Feature</b> shows the exploration of relativistic one- and four-component DFT methods for predicting hyperfine coupling constants in heavy heteroatom radicals. This study outlined in M. Witwicki’s Research Article (DOI: 10.1002/cphc.202400978) offers a practical blueprint for overcoming the computational challenges posed by these complex species, helping both computational chemists and experimentalists ascend the mountain range of difficulties and reveal the hidden electronic structure of heavy-element radicals.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202581002","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144100456","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electronic Excitation Transfer Dynamics in a 3-Site System Using an Incoherent Born-Markov Rate Model.","authors":"Amit Kumar Upadhyay, Karthik Sasihithlu","doi":"10.1002/cphc.202500029","DOIUrl":"10.1002/cphc.202500029","url":null,"abstract":"<p><p>The role of coherence in electronic excitation transfer (EET) dynamics in multi-site systems is typically investigated by comparing results from exact quantum dynamical methods with those derived from incoherent approaches such as the Fermi's Golden Rule (FGR) model. Recent studies on three-site systems have highlighted a remarkable dependence of EET dynamics on intersite coupling for specific configurations. To explore the influence of coherence in such behavior, we adapt the secular Redfield theory to develop an incoherent model by systematically excluding terms that couple populations and coherences in the site basis. The dynamics predicted by this model are then compared with those obtained from the coherent Lindbladian master equation and the incoherent FGR models. This framework provides a general approach for evaluating the role of coherence in a wide range of open quantum systems operating within the weak system-bath coupling regime.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500029"},"PeriodicalIF":2.3,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144101578","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}