Chemphyschem最新文献

{"title":"Effect of Charge Transfer and Solvation on X-Ray Absorption Near-Edge Spectra in Microsolvated Environment","authors":"Ninad Tirlotkar,&nbsp;Aryya Ghosh","doi":"10.1002/cphc.70576","DOIUrl":"10.1002/cphc.70576","url":null,"abstract":"<p>Electron delocalization in microsolvated clusters can substantially modify the character of electronic states accessed after core excitation. In this work, the K-edge XANES spectra of [Al(H₂O)<i>_n</i>]³⁺, with <i>n</i> = 1–6 complexes, are examined using the fc-CVS-EOM-CCSD and CVS-ADC(2)-x methods. We evaluate the influence of progressive hydration within first- and second-shell configurations on the core-excited electronic structure. Systematic variations occur in spectral properties for excitations into valence-like 3s, 3p, 4s, and 3d states. The charge–transfer analysis of representative 1s → 3p transitions indicates changes in spatial distribution and degree of excited-electron delocalization. Our results demonstrate the selective dependence of solvation geometry on governing the Al K-edge spectral features and the comparative application of highly correlated wave function approaches providing a method-resolved picture of the underlying microsolvation effect.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149104699","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 Electrolytic Water Performances of CuNi Alloy Foil Under the Surface Acoustic Waves","authors":"Cuihua An,&nbsp;Shize Ren,&nbsp;Shuang Chen,&nbsp;Tianhui Chen,&nbsp;Chunyou Zhu,&nbsp;Xiaolu Fan,&nbsp;Shuai Wu,&nbsp;Qibo Deng,&nbsp;Ning Hu","doi":"10.1002/cphc.70571","DOIUrl":"10.1002/cphc.70571","url":null,"abstract":"<p>Hydrogen production via water electrolysis faces challenges for large-scale commercial application due to its high electrical energy consumption, yet its immense potential warrants further in-depth investigation. Currently, a force–electrochemical coupling strategy employing external physical fields is emerging as a promising approach to assist both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). This work examines the HER and OER performances of a CuNi alloy electrocatalyst by applying surface acoustic waves (SAW) as an external physical field. The results demonstrate that SAW significantly enhances both HER and OER performances. For HER, the overpotential of the CuNi alloy at 10 mA cm⁻² was reduced by 29 mV under SAW, and the Tafel slope decreased from 115 to 101 mV dec⁻¹. For OER, the overpotential decreased from 430 to 390 mV, and the Tafel slope was notably reduced from 73.3 to 64 mV dec⁻¹. The performance enhancement is attributed to the accelerated adsorption of reactive hydrogen species during the HER and the optimized initial electron-transfer step in the OER induced by SAW. This optimization is likely mediated by SAW-induced interfacial lattice strain and the modulation of adsorption energetics for reaction intermediates.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149104692","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":"Comparing Homodimer and Homotrimer Noncovalent Complexes Involving Coinage Metals: A Theoretical Perspective","authors":"Sergi Burguera,&nbsp;Antonio Bauzá","doi":"10.1002/cphc.70585","DOIUrl":"10.1002/cphc.70585","url":null,"abstract":"<p>In this study, the geometry and physical nature of regium···regium contacts have been studied at the RI-PBE0-D4/def2-TZVPD level of theory. In more detail, diatomic M clusters (M = Cu, Ag, and Au) were used in a series of homodimer and homotrimer complexes, where they acted as both electron donor and acceptor counterparts. The results were analyzed using several state of the art quantum chemistry tools, such as the quantum theory of atoms in molecules (QTAIM), the natural nond orbital (NBO), the non-covalent interaction plot (NCIplot), and the energy decomposition analyses (EDA) methodologies. We believe the results reported herein will be useful for those scientists devoted to the field of physical chemistry, owing to the importance of molecular electronic structure in the formation of weak interactions.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13626965/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149104646","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":"Observation and Origin of Vertical Segment and Its Transition to Stable Slant Wire Formation via Metal–Mesh–Assisted Chemical Etching","authors":"Xiao-Qing Bao,&nbsp;Xiaohuang Yang,&nbsp;Yimeng Zhang,&nbsp;Xiaoguang Wang,&nbsp;Wei Li,&nbsp;Dehua Xiong,&nbsp;Kun Zhong,&nbsp;Jiahong Zhang,&nbsp;Zhiqun Cheng","doi":"10.1002/cphc.70548","DOIUrl":"10.1002/cphc.70548","url":null,"abstract":"<p>We report the temporal variation of slant angles across three distinct segments within a single wire at a fixed HF-to-H₂O₂ volume ratio <i>R</i> during metal-mesh-assisted chemical etching (MACE). This intrawire change in slant angle at a constant <i>R</i> differs fundamentally, in both phenomenon and mechanism, from the wire-to-wire variation in slant angles observed under varying <i>R</i> values. MACE of (100) Si substrate over extended durations typically yields tilted wires when using a medium-to-high <i>R</i>. Interestingly, while these structures appear slanted macroscopically, electron microscopy reveals a microscopic vertical segment at the uppermost portion of the wires. The underlying mechanism remains poorly understood. In this work, the existence of bubble-induced two-phase flow was confirmed indirectly by comparing stirred and unstirred MACE. The hydrogen produced by MACE initially remains dissolved, and after some time, bubbles start to nucleate and grow until they detach from the etching front. This characteristic three-stage gas evolution behavior was found to align well, in chronological order, with the vertical, curved, and slanted segments observed in the etched wires. To the best of our knowledge, this study offers the first interpretation linking gas evolution phases to intrawire morphology of macroscopically oblique wires produced by MACE.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149104696","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":"Structural and Spectroscopic Evidence of Hydrogen Bonded Anionic Wires in Protic Ionic Liquids","authors":"Maham Azhar,&nbsp;Lasse Hunger,&nbsp;Loai Al-Sheakh,&nbsp;Andreas Appelhagen,&nbsp;Lennart Kruse,&nbsp;Ralf Ludwig","doi":"10.1002/cphc.70581","DOIUrl":"10.1002/cphc.70581","url":null,"abstract":"<p>Hydrogen Bonding (H-bonds) between ions of like charge challenges the fundamental principle of electrostatics that opposite charges attract and like charges repel. This study provides direct structural and spectroscopic evidence of H-bonded anionic wires in protic ionic liquids (PILs), which consist of triethylammonium cations and hydrogen dicarboxylate anions. The anionic wires were identified by X-ray crystallography in the solid state, wherein the anions are linked by ⁻OH···O⁻ type H-bonds. The H-bonds within the anionic wire are significantly stronger than those between cation and anion despite repulsive Coulomb interaction in the first and attractive ones in the latter case. Analysis by nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy suggests that the binding motifs of the solid structure are mainly preserved in the liquid state of the supercooled PILs. This conclusion is drawn from density functional theory (DFT) calculations of the same structural motifs as observed in the solid state. The calculated ¹H NMR chemical shifts and IR C═O frequencies for these H-bond structures correspond well with the measured spectroscopic signatures. The anionic chains remain intact even when gradually removing the counterions. Our findings highlight the fundamental role of hydrogen bonding for the unusual attractive interaction between ions of like charge.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13624368/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149079997","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":"Corrigendum: Anisotropy Factor Spectra for Weakly Allowed Electronic Transitions in Chiral Ketones","authors":"","doi":"10.1002/cphc.70539","DOIUrl":"10.1002/cphc.70539","url":null,"abstract":"<p>Leon A. Kerber, Oliver Kreuz, Tom Ring, Hendrike Braun, Robert Berger, Daniel M. Reich<i>, Anisotropy Factor Spectra for Weakly Allowed Electronic Transitions in Chiral Ketones,</i> <i>ChemPhysChem</i>, <b>2025</b>, <i>26</i>, e202400898. https://doi.org/10.1002/cphc.202400898</p><p>The phases of the normal modes of vibration of the electronic ground state employed to determine the first derivatives of the electronic electric and magnetic dipole moments did not always align in our original publication with the phases of the normal modes of vibration of the electronic ground state used in the subsequent hotFCHT calculations. This was caused by an unintended additional diagonalization of the force constant matrix as a part of input preparation.</p><p>Aligning the phases led to an appreciable change in the spectra, slightly diminishing the agreement between our calculations and the experiment for 3-methylcyclopentanone (3MCP) and camphor, but strongly improving the agreement for fenchone. The corresponding corrected figures are shown below. Figure 1 replaces Figure 3 of the original publication. Figure 2 replaces Figure 4 of the original publication. Figure 3 replaces Figure 5 of the original publication. Figure 4 replaces Figure 6 of the original publication. Figure 5 replaces Figure 7 of the original publication. Figure 6 replaces the graphical abstract of the original publication. Our main conclusions, in particular the importance of Herzberg–Teller terms, were not affected by the phase alignment and are still evident in the new results.</p><p>In the original Supporting Information, the derivatives of the transition dipole moments for equatorial 3MCP were not presented in the Eckart frame of reference, a necessary condition for reproducing our results. Furthermore, the normal modes of vibration were listed therein in reverse order, resulting in incorrect wavenumber assignments (i.e., the <b><i>l</i></b>-matrix coefficients of the highest wavenumber modes were associated with the lowest wavenumbers). To ensure this corrigendum is self-contained, Table 1 reports the vibrational modes where phase changes occurred. Tables 2 and 3 present the corrected first derivatives of the electric and magnetic transition dipole moments for equatorial 3MCP. A fully revised version of the Supporting Information is also provided.</p><p>The authors apologize for this oversight.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.70539","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149079987","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":"An Ultrathin Hydroxide Film Governs the Stability and Reactivity of Gold for the Oxygen Evolution Reaction","authors":"A. Grespi,&nbsp;A. Larsson,&nbsp;A. Ti,&nbsp;V. Briega-Martos,&nbsp;E. Lira,&nbsp;U. Küst,&nbsp;G. Abbondanza,&nbsp;J. Manidi,&nbsp;S. Cherevko,&nbsp;A. Shavorskiy,&nbsp;M. Scardamaglia,&nbsp;M. Ramakrishnan,&nbsp;J. Just,&nbsp;L. R. Merte,&nbsp;E. Lundgren","doi":"10.1002/cphc.70567","DOIUrl":"10.1002/cphc.70567","url":null,"abstract":"<p>Surface oxidation of noble metals under electrochemical conditions has a decisive impact on the performance of electrocatalysts for electrolyzers and fuel cells. However, the experimental detection of such oxides on well-defined model electrodes under operando conditions is a major challenge, limiting our ability to establish clear structure–performance relationships. Using surface-sensitive total-reflection X-ray absorption spectroscopy in real time during cyclic voltammetry, combined with inductively coupled plasma mass spectrometry dissolution measurements, we demonstrate that an ultrathin (~5 Å) hydroxide film forms on the gold (111) surface prior to the onset of the oxygen evolution reaction. This film, composed of Au³⁺ in similar coordination as in the bulk oxyhydroxide, thus governs its catalytic properties, dissolution, and restructuring. The results highlight the importance of surface oxidation in water splitting catalysis even for Au(111), the most inert surface of the most inert noble metal.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.70567","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149073653","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":"Quantum and Quasiclassical Dynamics of the S + SD Reaction: Role of Reagent Vibrational Excitation","authors":"Suraj Kumar,&nbsp;Sakshi Yadav,&nbsp;A. J. C. Varandas,&nbsp;Tammineni Rajagopala Rao","doi":"10.1002/cphc.70577","DOIUrl":"https://doi.org/10.1002/cphc.70577","url":null,"abstract":"<p>The S(³<i>P</i>) + SD(<i>X</i>²Π) reaction is investigated on the ground electronic HS₂ potential energy surface (PES) using time-dependent wave packet (TDWP) and quasiclassical trajectory (QCT) methods. Initial state-selected reaction probabilities and integral cross sections are calculated for abstraction and exchange channels at collision energies up to 0.10 eV. Both channels proceed without an entrance barrier through an intermediate complex, with abstraction being the dominant pathway owing to the high stability of S₂. The role of reactant vibrational excitation is examined for <i>ν</i> = 0, 1, 3, 5, and 10, with <i>j</i> = 0. For <i>ν</i> = 0, the quantum results agree well with the classical trajectories, indicating the reaction is governed primarily by classical forces. A QCT/QM-<i>α</i>J extrapolation scheme is assessed against full quantum results and provides an efficient and reliable approach for estimating integral cross sections while retaining essential quantum effects. For the exchange channel, the quantum cross sections show a gradual enhancement at higher collision energies from <i>ν</i> = 1, while the abstraction channel shows this enhancement only from <i>ν</i> = 5 onward. At <i>ν</i> = 10, they stop decreasing: the abstraction cross section increases with collision energy, whereas the exchange cross section levels off. These results demonstrate that quantum effects become important at high vibrational excitation.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 19","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149029054","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":"Applications of Hollow Carbon-Based Materials in Heterogeneous Advanced Oxidation Processes for Antibiotic Degradation: A Critical Review","authors":"Yu-Fei Zhen,&nbsp;Zeng Li,&nbsp;Yu Tian,&nbsp;Jun Ma,&nbsp;Cheng-Yan Xu","doi":"10.1002/cphc.202500801","DOIUrl":"10.1002/cphc.202500801","url":null,"abstract":"<p>The expanding pharmaceutical industry has led to the widespread detection of antibiotics in various aquatic environments, posing a significant ecological risk and threatening public health. Heterogeneous advanced oxidation water treatment processes (AOPs) for pollutant removal by generating reactive oxygen species (ROS) offer a promising solution. Currently, the pivotal challenge lies in the development of efficient and green catalysts. Hollow carbon-based materials (HCMs) have attracted extensive attention in inducing heterogeneous AOPs for antibiotic removal due to their unique physicochemical properties. The hierarchical porous and hollow structure endows it with significant advantages such as the ability to efficiently enrich reactants, provide a large number of active sites, and have a flexible and adjustable electronic structure, demonstrating excellent catalytic activity and stability. This review makes a comprehensive survey of the progress of HCMs in the removal of antibiotics in heterogeneous AOPs in recent years, focusing on their structural design, synthesis methods, and the vital mechanisms of performance optimization, such as cavity confinement effects. In addition, their application as heterogeneous catalysts in the degradation of antibiotics in AOPs, including persulfate (PS) activation, photo-Fenton catalysis, and catalytic ozonation, was discussed, with the underlying reaction mechanisms revealed. Finally, we outline future research directions and challenges faced by hollow carbon-based catalysts in heterogeneous AOPs, offering valuable insights for further development of water treatment strategies.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 18","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149036297","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":"Understanding the Effect of Amino Acid Conjugation on Optoelectronic Properties of Graphene Quantum Dots: Insights From DFT and TD-DFT Analysis","authors":"Kaushik Sen,&nbsp;Soumitra Ghorai,&nbsp;Debjani Nag","doi":"10.1002/cphc.70572","DOIUrl":"10.1002/cphc.70572","url":null,"abstract":"<p>Graphene quantum dots (GQDs) have attracted immense attention from both academia and industry as an advanced nanoscale carbon material having widespread applications. Attributes like unique optical and electronic properties, nontoxicity, solubility, and biocompatibility make them desirable candidates for drug delivery and cell-targeted bioimaging. Suitability of GQDs for these coveted applications can be improved through conjugation with amino acid systems. Influence of amino acid conjugation on the optoelectronic features of GQDs therefore needs to be analyzed clearly. To this end, quantum chemistry investigations within the framework of DFT and TD-DFT calculations have been carried out in the present work. The amino acids have been classified and scrutinized based on their side chain polarity, aromatic, and aliphatic contents. Our calculation interestingly reveals that amino acid-containing nonpolar side chain along with heterocyclic aromatic component favors a redshift in the near infrared (NIR) region of the absorption spectrum. This fosters the suitability of GQDs for biomedical applications. Our work also illustrates that tuning the polarity of the side chains normally tends to produce a blueshifted spectrum. Thus, amino acid conjugation of GQDs offers “plenty of room at the bottom” for us to explore further and provide rational guidance using quantum chemistry techniques.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 18","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149036414","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}