Chemphyschem最新文献

{"title":"Stress Effectively Enhances the Ferromagnetic Stability of Monolayer NiZr.","authors":"Weifu Cen, Nuanxu Wang, Yixuan Wang, Ping Zou","doi":"10.1002/cphc.202500813","DOIUrl":"10.1002/cphc.202500813","url":null,"abstract":"<p><p>Stress is extensively utilized to regulate the electronic structure and associated physical properties of two-dimensional materials. As a high-temperature alloy, Monolayer nickel-zirconium (NiZr) exhibits unstable ferromagnetism in the absence of external stress. Nevertheless, the stability of its ferromagnetic state is significantly enhanced under applied stress, where tensile stress induces an increase in magnetic moment. The effect of stress on the magnetic moment can be attributed to variations in the band structure. Specifically, the band structure of monolayer NiZr, which is characterized by stable ferromagnetism under stress, and exhibits both semiconductor and semi-metallic characteristics. This variation in band structure originates from spin fluctuations among d and p electrons, which are influenced by the surrounding potential field. In detail, d and p orbitals form nonorthogonal linear combinations such as p_z-d_xx-yy, p_x-d_zx, and p_y-d_yz. The stress-induced modulation of magnetic properties is primarily manifested through the response of the d_zx and d_zy spin orbitals. With an increase in tensile stress, the occupancy of the d_zy orbital increases correspondingly, while the spin orientation of other orbitals is reversed, simultaneously. Notably, under tensile strain, the occupancy of the d_zx spin orbital increases, whereas that of the d_zy spin orbital decreases. In contrast, the changes in other orbitals remain relatively negligible under compressive stress. Consequently, this phenomenon leads to variations in orbital coupling, as well as in distributions within both orbital space and spin charge space. Under stress, the coupling between d and p orbitals results in the formation of σ bonds and π bonds. The interaction between p orbitals and σ bonds is significantly stronger than that between p orbitals and π bonds, and this discrepancy constitutes one of the primary factors driving the stress-induced changes in the magnetic properties of monolayer NiZr.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 8","pages":"e202500813"},"PeriodicalIF":2.2,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147728610","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":"First-Principles Study of Nonlinear Optical Properties of Pristine and Substrate-Supported SnS, SnSe, and SnTe Monolayers.","authors":"Ashima Rawat, Ravindra Pandey","doi":"10.1002/cphc.202500870","DOIUrl":"https://doi.org/10.1002/cphc.202500870","url":null,"abstract":"<p><p>2D monolayers of tin monochalcogenides (SnX, with X = S, Se, and Te) offer environmental stability, making them promising for various technological applications. Although proposed as ferroelectrics, their nonlinear optical (NLO) activity has not been fully explored. Here, we use density functional theory to quantify their NLO response by calculating the (hyper)polarizability. These monolayers are semiconducting and form a stable Type II heterostructure with TiO₂(001), which is advantageous because it effectively suppresses electron-hole recombination in a device. The interfacial electronic states, created by the interaction of the (Sn) lone pair electrons with the substrate's electronic states, lead to increased polarizability (α) and first dipole hyperpolarizability (β) of the supported monolayers. Additionally, a significant enhancement in both β (-ω; ω, 0); β (0; 0, 0), and β (-2ω; ω, ω) is predicted for the supported SnSe monolayer. This may be due to a resonance effect associated with an interfacial charge-transfer transition, which appears to be closely aligned with the incident photon energy at λ = 1064 nm. This overall amplification of the NLO response indicates that these supported chalcogenide monolayers are promising candidates for next-generation nanoscale photonic technologies.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 8","pages":"e202500870"},"PeriodicalIF":2.2,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147763838","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":"Visible-Light-Driven Spontaneous Water Splitting in a 2D Janus WSSe/GaO Z-Scheme Heterostructure.","authors":"Lu Liu, Liang Xu, Qiyun Wang, Zhenwu Jin, Yifan Yang, Yi Li, Ling-Ling Wang, Kejun Dong","doi":"10.1002/cphc.202500893","DOIUrl":"https://doi.org/10.1002/cphc.202500893","url":null,"abstract":"<p><p>Solar-driven photocatalytic water splitting is a pivotal technology for global carbon neutrality, with the core challenge being the development of efficient, stable photocatalysts operating without sacrificial agents. Two-dimensional (2D) Z-scheme heterostructures are promising for efficient charge separation, while Janus materials with intrinsic polarization offer unique opportunities to enhance photocatalytic performance. Herein, we systematically investigate a 2D Janus WSSe/GaO heterostructure constructed from Janus WSSe and GaO monolayers via first-principles calculations. The results demonstrate that the heterostructure exhibits a high electron mobility of 1864.53 cm² V^-1 s^-1 and broadband visible-light absorption. Owing to its Z-scheme band alignment, the heterostructure enables spontaneous water-splitting hydrogen production under neutral or acidic conditions, achieving a theoretical solar-to-hydrogen conversion efficiency of 20.99%-surpassing most reported 2D heterostructures. This work highlights the potential of Janus-based Z-scheme heterostructures for high-performance photocatalysis and provides a theoretical basis for experimental fabrication.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 8","pages":"e202500893"},"PeriodicalIF":2.2,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147763413","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":"Paired Electrosynthesis: Concurrent Production of V^3.5+ Electrolyte for Vanadium Redox Flow Battery and p-Chlorobenzaldehyde in a Flow Microreactor.","authors":"Liyun Huang, Linshuai Wang, Wangyan Zhang, Gang Xie, Xiaojie Liu, Liping Cao, Ying Yang","doi":"10.1002/cphc.202600006","DOIUrl":"https://doi.org/10.1002/cphc.202600006","url":null,"abstract":"<p><p>This work addresses the preparation of V^3.5+ electrolyte for vanadium redox flow batteries (VRFBs) by proposing an efficient paired electrosynthesis strategy, combining it with the synthesis of the high-value-added chemical p-chlorobenzaldehyde (PCAD). Traditional methods for preparing V^3.5+ electrolyte suffer from issues like impurity introducing and low energy utilizing, while the hydrogen reduction reaction at the cathode in PCAD synthesis has low value. To solve these problems, this work designed and constructed a paired electrosynthesis system based on an electrochemical microchannel reactor: precisely reducing VOSO₄ to V^3.5+ electrolyte at the cathode, while simultaneously electro-oxidizing Mn²⁺ to Mn³⁺ at the anode, which subsequently oxidizing p-chlorotoluene (PCT) to synthesize PCAD. The effects of current density, sulfuric acid concentration, and reactant ratio on reaction efficiency were systematically investigated. Results show that the total vanadium valence state of the cathodically prepared V^3.5+ electrolyte stabilized at 3.50 ± 0.02, the yield of anodically synthesized PCAD was 35.51%, the total current efficiency of the paired electrosynthesis system reached 178.8%, and the system demonstrated good repeatability and stability. This study provides a new approach for the green and efficient preparation of VRFB electrolytes and the electrosynthesis of high-value chemicals.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 8","pages":"e202600006"},"PeriodicalIF":2.2,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147763850","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":"Resolving the Puzzling Observations in Trapping Dynamics of Polystyrene and Silica Microparticles Under Femtosecond Pulsed and Continuous-Wave Excitations.","authors":"Abdul Alim, Sumit Yadav, Arijit K De","doi":"10.1002/cphc.202500910","DOIUrl":"https://doi.org/10.1002/cphc.202500910","url":null,"abstract":"<p><p>We set out to resolve a long-standing dilemma regarding the contradictory claims for the less or equal effectiveness of high-repetition-rate ultrashort pulsed excitation compared with continuous-wave (CW) excitation in optical trapping of dielectric microparticles. We present a comparative analysis of the trap stiffness of polystyrene and silica microparticles under CW and femtosecond pulsed excitation. We investigate how optical nonlinearity influences trap stiffness and highlight the distinct responses exhibited by polystyrene and silica particles under different excitations. Our results explain previous confounding results of trap stiffness under pulsed excitation compared to CW excitation in optical trapping of microscopic particles.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 8","pages":"e202500910"},"PeriodicalIF":2.2,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147763829","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":"Quantification of Intramolecular (-) and (+) Charge-Assisted Hydrogen Bond Energy via Molecular Tailoring Approach: Ranking in Energy Scale.","authors":"Andrei V Afonin, Danuta Rusinska-Roszak","doi":"10.1002/cphc.70390","DOIUrl":"https://doi.org/10.1002/cphc.70390","url":null,"abstract":"<p><p>The energies of O-H···O^- and N⁺-H···O charge-assisted hydrogen bonds quantified via the method based on molecular tailoring approach for a series of anionic and cationic compounds. The energies of O-H···O^- and N⁺-H···O charge-assisted hydrogen bonds vary from 15 to 43 and from 5 to 29 kcal/mol, being five and seven times stronger, on average, respectively, than conventional intramolecular hydrogen bonds in neutral prototypes. The strengthening of (-) and (+) charge-assisted hydrogen bonds in anions and cations relative to conventional hydrogen bonds in neutral compounds is accompanied by significant changes in the structural, spectral and theoretical hydrogen bond descriptors. The hydrogen bond geometry changes, the spectral manifestations of (-) and (+) charge-assisted hydrogen bonds and process of electron transfer through hydrogen bond become more pronounced compared to conventional hydrogen bonds. The energies of (-) and (+) charge-assisted hydrogen bonds and conventional hydrogen bonds are functionally related to the values of hydrogen bond descriptors, allowing the former to be evaluated using the latter. It has been shown that the energies of (-) and (+) charge-assisted hydrogen bonds are the strongest of the known types of hydrogen bonds and belong in most cases to the category of strong hydrogen bonds.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 8","pages":"e70390"},"PeriodicalIF":2.2,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147763834","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":"Probing Composition Effects on the Intrinsic Energetics of Proton Transfer in Binary (HCl)_m(H₂O)_n Clusters.","authors":"Max R Tucker, Sarah N Arradondo, Olivia M Longsworth, George C Shields, Gregory S Tschumper","doi":"10.1002/cphc.202500920","DOIUrl":"https://doi.org/10.1002/cphc.202500920","url":null,"abstract":"<p><p>This work examines the effects on intrinsic energetics as the composition of finite (HCl)_m(H₂O)_n cluster families containing at least one water molecule is changed at the molecular level, where m ≥ 2 and m + n = 4 - 6, and the associated (Cl^-)_x(H₃O⁺)_x(HCl)_m-x(H₂O)_n-x clusters resulting from the dissociation of x HCl fragments via proton transfer (PT). They are collectively labeled m:n, and xPT indicates the degree of dissociation, from 0PT (no dissociation) up to 3PT. More than 1000 unique minima were identified via ωB97X-D/6-31++G(d,p) optimizations and frequency computations. Of those, nearly 500 lie within 5 kcal mol^-1 of the corresponding lowest-energy minimum structure as determined by CCSD(T)-F12/haTZ-F12 single point energies: 25 for the 2:2 and 3:1 tetramers, 127 for the 2:3, 3:2, and 4:1 pentamers, and 333 for the 2:4, 3:3, 4:2, and 5:1 hexamers. In four of the nine m:n systems examined (2:2, 3:1, 4:1, 5:1), no low-energy minima exhibited PT, but the other five (2:3, 3:2, 2:4, 3:3, 4:2) have 1PT and 2PT structures with electronic energies near or below the lowest-energy 0PT configurations. In the 2:4, 3:3, and 4:2 hexamers, for example, at least one 1PT structure lies ≈4, 3, and 0.5  kcal mol^-1 below the lowest-energy 0PT structures, respectively, based on CCSD(T)-F12 electronic energies.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 8","pages":"e202500920"},"PeriodicalIF":2.2,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13110105/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147763847","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":"From the Modeling of Experiments to the Ab Initio Prediction of Rate Constants: Statistical Rate Theory for a Quantitative Understanding of Gas-Phase Ion Chemistry.","authors":"Thomas Auth, Konrad Koszinowski","doi":"10.1002/cphc.70362","DOIUrl":"10.1002/cphc.70362","url":null,"abstract":"<p><p>Statistical rate theory has long been used for the analysis of gas-phase ion reactions. Traditionally, it has mainly served as a framework for fitting experimental data, often obtained with highly specialized instrumentation, and extracting quantities of interest, such as reaction threshold energies. With the progress in quantum chemical calculations and their ability to provide accurate energy profiles along reaction coordinates, the reliable ab initio prediction of rate constants of gas-phase ion reactions appears to be within reach. Such predictions would be quite valuable, because they enable the direct comparison between the results from theory and standard mass-spectrometric experiments and, thus, aid in the interpretation of the latter. In this review, we seek to answer the question of the extent to which accurate ab initio predictions of gas-phase ion reaction rate constants have become feasible and can be used for routine applications. After covering the basics of statistical rate theory and giving an overview of important programs for rate calculations, we demonstrate and discuss the current state of the field for four different examples: the dissociation of the n-butylbenzene radical cation, the dissociation of benzylpyridinium ions, the unimolecular reactivity of anionic organometallic complexes, and the reactivity of organometallic ions toward proton donors.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 8","pages":"e70362"},"PeriodicalIF":2.2,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13096677/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147728489","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":"Correlated Incorporation and Structural Variability in Au-CdSe/CdS Plasmon-Exciton Hybrid Microspheres.","authors":"Parineeta Gogoi, Payal Taneja, Lakshmi Madathil, Gopika Prasad, Nikita Tanwar, Anshu Pandey","doi":"10.1002/cphc.202500881","DOIUrl":"https://doi.org/10.1002/cphc.202500881","url":null,"abstract":"<p><p>Structural distribution of semiconductor quantum dots (QDs) and plasmonic metal nanostructures in assemblies determines the emergent light-matter interactions and thus is extremely important. Here, we systematically investigate the structural aspects of self-assembly of thiol-capped Au nanoparticles and CdSe/CdS QDs into hybrid microspheres at various component ratios. Composition-dependent morphology of Au-QD hybrids is confirmed by transmission electron microscopy and energy-dispersive X-ray spectroscopy (EDS). Statistical analysis of the EDS data shows that the incorporation differs from Poisson statistics, consistent with chemical and structural effects guiding and controlling key aspects of the assembly process. In addition, the Gini index and Moran's I were used to measure the compositional heterogeneity and spatial clustering, respectively, revealing that Au is still uniformly dispersed while CdSe/CdS regions accumulate in more localized domains. This work offers a quantitative understanding of the statistical nature of nanocrystal incorporation and shows the routes to structural deterministic plasmon-exciton hybrid architectures.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 8","pages":"e202500881"},"PeriodicalIF":2.2,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147763763","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":"Investigating Synthetic Dolomite Mixtures and Phase Adjustment Parameters in Electrochemical Cement Precursor Production.","authors":"Anthony R Ramuglia, Phong V Ly, Sophie Hurst-Fraunhofer, Julius Scheel, Kelly Henze, Thomas Köberle, Volodymyr Bon, Stefan Kaskel, Viktor Mechtcherine, Thomas Matschei, Marco Liebscher, Inez M Weidinger","doi":"10.1002/cphc.202500809","DOIUrl":"https://doi.org/10.1002/cphc.202500809","url":null,"abstract":"<p><p>The precursor material of Portland cement (PC) colloquially referred to as clinker is produced primarily via calcination of limestone (CaCO₃). Magnesia-based cements can similarly be formed via calcination of magnesite (MgCO₃) among other routes. Dolomitic minerals typically contain a mixture of these carbonate mineral phases. The current study monitors and explores the electrochemical transformation of CaCO₃ and MgCO₃ synthetic mixtures approximating dolomite and investigates their applicability in forming cementitious phases. The transformation of such mixtures indicates that Mg- and Ca-based electrolysis products, namely Ca(OH)₂ and Mg(OH)₂, respectively, display different precipitation parameters. Mg(OH)₂ precipitates more rapidly in the form of flower-shaped micro-aggregates, while Ca(OH)₂ forms slower in comparison, precipitating in larger hexagonal prismatic structures. These findings point toward possible mixture separation techniques for PC and magnesia-based cements.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 8","pages":"e202500809"},"PeriodicalIF":2.2,"publicationDate":"2026-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13102320/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147763771","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}