Physical Chemistry Chemical Physics最新文献

{"title":"Spin-orbit coupling effects hidden behind the photophysics of phosphorescent chiral cyclometalated Pt(II) complexes","authors":"Thomas Groizard, Souvik Mandal, Christophe Gourlaouen, Chantal Daniel","doi":"10.1039/d5cp01450f","DOIUrl":"https://doi.org/10.1039/d5cp01450f","url":null,"abstract":"The electronic and (chiro-) optical properties of [Pt(pCpy)(acac)] 1 and [Pt(pCpz)(acac)] 2 (pCpy = 2-[2,2]-paracyclophane-4-yl) pyridyl; pCpz = 1-[2,2]-paracyclophane-4-yl) pyrazolyl; acac = dimethyl-substituted acetylacetonato), representative of phosphorescent chiral cyclometalated Pt(II) complexes, are investigated by means of density functional theory (DFT) and it’s time-dependent extension so-called TD-DFT, including spin-orbit coupling (SOC) effects. The computed absorption, phosphorescence and circularly polarized luminescence (CPL) spectra are compared to the available experimental spectra, when available, and analysed on the basis of spin-orbit interactions and electronic excited state sub-levels. The major role of the SOC is established and deciphered for both complexes. Spin-orbit sub-levels of the low-lying triplet manifold do not only perturb the absorption spectra by a 60-70 nm shift to the red, but entirely control the phosphorescence and CPL activities, in terms of intensity and composition. It is shown that the substitution of a pyridyl ligand in 1 by a pyrazolyl in 2 has dramatic consequences on the photophysics of these “case-study” molecules. Indeed, the character and the energetics of the lowest triplet states participating to the emission properties is drastically affected by this change of ligands. Whereas [Pt(pCpy)(acac)] 1 can be considered as an “easy case”, both experimentally and theoretically, [Pt(pCpz)(acac)] 2 represents a challenge computationally due to the presence of two nearly degenerate emissive triplet states. The correlation between the structural / electronic properties of the excited states contributing to the spectra is discussed as well as the early time (< 1 ps) photophysics simulated by non-adiabatic quantum dynamics for the two complexes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"218 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260639","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":"Square octagon haeckelites as efficient photocatalysts with enhanced solar-to-hydrogen conversion and high carrier mobilities","authors":"Ismail Shahid, Iqtidar Ahmad, Anwar Ali, Abid Raza, Xiaoliang Zhang, Dawei Tang, Mohamed Kallel, Shaimaa A. M. Abdelmohsen","doi":"10.1039/d5cp01522g","DOIUrl":"https://doi.org/10.1039/d5cp01522g","url":null,"abstract":"The increasing demand for renewable energy solutions underscores the importance of photocatalytic water splitting as a sustainable technology. In this study, we present a first-principles investigation of synthesized novel square-octagon haeckelite AB compounds (A = Sb, Be, Cd, In, Mg, Zn; B = Al, S, Se, Te, P), revealing their superior photocatalytic properties. These 3D materials exhibit unique square-octagonal geometries, optimized band gaps (1.33–3.83 eV), and favorable band edge alignments for water splitting under both acidic (pH = 0) and neutral (pH = 7) conditions. Notably, AlSb achieves the highest solar-to-hydrogen efficiency of 49.00%, followed by CdTe (38.97%), CdSe (18.35%), and InP (38.21%), outperforming conventional photocatalysts. The study also highlights the exceptional carrier mobilities (<em>μ</em>) of AB haeckelite compounds, with ZnTe achieving an electron mobility of 19.3 × 10<small>⁶</small> cm<small>²</small> V<small>⁻¹</small> s<small>⁻¹</small> and hole mobility of 24.9 × 10<small>⁴</small> cm<small>²</small> V<small>⁻¹</small> s<small>⁻¹</small>. These high mobilities facilitate efficient charge transport and minimize recombination losses, enhancing their photocatalytic performance. Additionally, CdTe and CdSe demonstrate strong visible-light absorption, while MgSe and BeSe excel in ultraviolet absorption, showcasing their versatility for optoelectronic applications. This work establishes AB haeckelite compounds as transformative materials for solar-driven hydrogen production by overcoming conventional photocatalysts' limitations, like poor sunlight utilization and low carrier mobility, paving the way for sustainable energy technologies.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"5 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260641","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":"Regulation of protein translocation through A Si3N4-CNT stacked nanopore using an embedded gold nanoparticle","authors":"Wei Si, Haonan Chen, Gensheng Wu","doi":"10.1039/d5cp01017a","DOIUrl":"https://doi.org/10.1039/d5cp01017a","url":null,"abstract":"Proteins play a crucial role in the growth, movement, and reproduction of life, and the determination of accurate protein sequences is of great significance in understanding the specific functions of proteins. Nanopore sequencing is currently the most prevalent method due to its speed, cost-effectiveness, and ability to sequence long proteins. However, its accuracy is often compromised by the rapid translocation of the sample, making it challenging to generate effective blocking signals. To address this, a protein translocation regulation device is proposed in this paper. The primary component of this device is a carbon nanotube on a silicon nitride membrane, with two holes in its sidewall to facilitate the lateral passage of proteins. Further, we have incorporated a gold nanoparticle into the carbon nanotube, which can be controlled to move within it. By manipulating the position of the gold nanoparticle, we can alter the conformation of the proteins inside the nanotube, thereby achieving varying degrees of speed reduction. In addition, we made the gold nanoparticle positively charged in our simulation environment. Under the effect of electroosmotic flow, we realized better speed reduction. This proposed device holds significant potential for large-scale protein down-rate sequencing in the future.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"10 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260645","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":"Modeling the Projected Range of Protons in Matter: Insights from Molecular Dynamics and Quantum Chemistry","authors":"Chieh-Min Hsieh, Alexander Dellwisch, Tim Neudecker","doi":"10.1039/d5cp00223k","DOIUrl":"https://doi.org/10.1039/d5cp00223k","url":null,"abstract":"Estimating the projected range of high-energy particles is important for ion implantation and designing shielding strategies for space devices. In this work, we propose a molecular dynamics (MD) workflow to calculate the projected range of protons and demonstrate its capabilities by calculating the projected range of protons in graphite and poly(methylmethacrylate) (PMMA). The results show excellent agreement with reference data. Besides, we investigate irradiation-induced bond breaking by simulating the proton bombardment of a perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecule and analyze the strain energy accumulated in the system using quantum chemical tools. The findings indicate a correlation between strain energy and the kinetic energy of the primary knock-on atom.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"219 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260691","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":"To Mix or Not to Mix: Charge and Polarity Effects on Alkyl/Fluoroalkyl Compound Miscibility§","authors":"Joshua Lai, Evelyn F. Gladden-Bennett, Karina Shimizu, Naomi Elstone, Theo Tanner, Bruno Demé, Adrian Charles Whitwood, Seishi Shimizu, José N.C Lopes, John M. Slattery, Duncan W Bruce","doi":"10.1039/d5cp01737h","DOIUrl":"https://doi.org/10.1039/d5cp01737h","url":null,"abstract":"The (im)miscibility of hydrocarbons and perfluorocarbons is well known, depends on the chain lengths involved and has been widely exploited in many different areas of chemistry. One area where mixing hydrocarbon- and fluorocarbon-containing moieties is of current interest is in ionic liquids (ILs) ,where physicochemical properties may be tuned via the preparation of mixtures. Recent work has shown that mixtures of the imidazolium ILs [C<em><small>_n</small></em>MIM][Tf<small>₂</small>N] and [C<em><small>_n</small></em>MIM-F<small>_{<em>2</em>+12}</small>N] (<em>m</em> = n–2) are miscible when a perfluorooctyl chain is used (n = 8), which is unexpected at this chain length. In order to explore the influence of electrostatic attraction between ions in this observed miscibility, related, neutral N-substituted imidazoles CnIm and CnIm-F2m+1 employing hydrocarbon and semiperfluorocarbon chains, and their mixtures, were prepared. The mixtures were miscible at room temperature for n = 8 and immiscible for n = 10. The miscible mixtures were investigated by surface tension, small-angle X-ray and neutron scattering methods and by atomistic molecular dynamics simulations. The data show that while the mixtures [C<small>₈</small>Im]<small>_{1–<em>x</em>}</small>[C<small>₈</small>Im-F<small>₁₃</small>]<small>_<em>x</em></small> are continuously miscible, some preferential aggregation of alkyl and fluoroalkyl chains is nonetheless present, mirroring the behaviour observed for the IL mixtures [C<small>₁₀</small>MIM]<small>_{1–<em>x</em>}</small>[C<small>₁₀</small>MIM-F<small>₁₇</small>]<small>_<em>x</em></small>[Tf<small>₂</small>N], yet in contrast to the shorter-chain mixtures [C<small>₈</small>MIM]<small>_{1–<em>x</em>}</small>[C<small>₈</small>MIM-F<small>₁₃</small>]<small>_<em>x</em></small>[Tf<small>₂</small>N] where no aggregates are seen. As such, it has been possible to draw some conclusions concerning the ability of electrostatic interactions between the ions to suppress the otherwise expected immiscibility of the alkyl and fluoroalkyl chains.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260626","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":"Interlayer coupling of valley and layer in homostructure bilayer ScI2","authors":"Xiao-Jing Dong, Chang-wen Zhang","doi":"10.1039/d5cp01131k","DOIUrl":"https://doi.org/10.1039/d5cp01131k","url":null,"abstract":"Despite transformative progress in valleytronic manipulation via heterostructure engineering, the valley-layer coupling mechanisms in homostructure two-dimensional (2D) systems remain a fundamental challenge. Here, we construct a homostructure bilayer ScI2 and find that it exhibits both ferroelectricity and ferrovalley properties, with its valley polarization tunable via interlayer sliding symmetry. Interlayer sliding from AB to AC stacking requires only 14.7 meV energy, yet drives an appreciable 114 meV valley polarization alongside robust out-of-plane ferroelectric polarization reaching 3×10⁻¹¹ C/m. Specially, the Curie temperature of bilayer ScI2 reaches up to 615 K, making it favorable for applications at room temperature. Also, the valley-layer interplay in ScI2 homostructure drives a layer-locked anomalous Hall effect with electrically switchable polarization. The coupled valley and layer degrees of freedom in ScI2 bilayers establish a sliding symmetry-protected mechanism for valley polarization materials in homostructures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"102 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260644","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":"Deep-Blue Thermally Activated Delayed Fluorescence from a CF3-substituted Carbene-Metal-Amide Complex","authors":"Alexander C. Brannan, Nguyen Le Phuoc, Mikko Linnolahti, Alexander S. Romanov","doi":"10.1039/d5cp00824g","DOIUrl":"https://doi.org/10.1039/d5cp00824g","url":null,"abstract":"The gold-based carbene-metal-amide (CMA) complex BICAuBGCF3 with a 2-(trifluoromethyl)-benzoguanidine amide (L) have been prepared in good yields and characterized. The CF3-substituted amide donor ligand resulted in 0.27 eV stabilization of the highest occupied molecular orbital (HOMO) and wide energy gap of 2.97 eV. In fluid media complex experience a dynamic behavior between two forms which reduces the blue luminescence quantum yield down to 43%. In solid state complex shows bright deep-blue thermally activated delayed fluorescence at 432 nm with 60% luminescence quantum yield thanks to small singlet triplet energy gap (ΔEST) down to 54 meV. The radiative rates (kr) are up to 1.4×106 s–1 in amorphous polystyrene media indicating BICAuBGCF3 complex as a promising material for optoelectronic applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"11 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260640","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":"Solvation dynamics of electron-metal cation contact pairs in LiCl aqueous solutions","authors":"Denis Dobrovolskii, M. Mostafavi, Sergey A. Denisov","doi":"10.1039/d5cp01480h","DOIUrl":"https://doi.org/10.1039/d5cp01480h","url":null,"abstract":"In this study, the dynamics of the solvation of (Li+-electron) pairs were investigated in LiCl water solutions at concentrations from 2 to 14.6 M. The dynamics of contact pair solvation were observed for the first time experimentally using picosecond electron radiolysis. We observe a clear concentration-dependent increase in electron solvation time, from 10.6 ps at LiCl 3.5 M to 17.3 ps at 14.6 M. We discuss a descriptive mechanism of such a solvation in the presence of metal cations.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"24 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260642","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 careful scrutiny of the aromaticity in anionic polynitrogen clusters","authors":"Gourhari Jana, Pratim Chattaraj","doi":"10.1039/d5cp01974e","DOIUrl":"https://doi.org/10.1039/d5cp01974e","url":null,"abstract":"The aromaticity of polynitrogen clusters plays a crucial role in defining their stability and potential applications in high-energy materials. In this study, we provide a comprehensive assessment of the aromatic character of N42- and N64- using a multifaceted approach that combines nucleus-independent chemical shift (NICS) analysis and the zz component of the magnetic shielding tensor. To further unravel the intricate electronic structures of these clusters, we employ state-of-the-art electronic descriptors, including the electron localization function (ELF) and adaptive natural density partitioning (AdNDP). Moreover, the propensity of these polynitrogen species for π-stacking interactions is meticulously evaluated using the Localized Orbital Locator Integrated Pi Over Plane (LOLIPOP) method. Our findings offer valuable insights into the fundamental electronic nature of polynitrogen clusters, shedding light on their stability and potential for supramolecular assembly.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"7 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252039","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":"Investigations of water-induced polar facet stabilization mechanism in ZnO nanoplates with 1H NMR spectroscopy","authors":"benteng Song, Qin Zhu, Ling-Hai Xie","doi":"10.1039/d5cp01005e","DOIUrl":"https://doi.org/10.1039/d5cp01005e","url":null,"abstract":"ZnO with polar facets has been extensively studied in material sciences due to its wide applications. However, the stabilization mechanisms for polar surfaces in ZnO nanomaterials are still unclear. Here, we show that water can dissociate at Zn and O vacancy on polar (0001)-Zn and (0001 @#x0305;)-O surface of ZnO nanoplates, respectively, producing H in Zn vacancy and surface OH groups. Upon exposure to saturated water vapor, in addition to the peak arising from H in Zn vacancy, the amount of surface OH species increases owing to water dissociation on both polar Zn- and O-terminated surfaces, resulting in significant electrostatic repulsion between these polar surfaces. This improves the dispersity of ZnO nanoplates and thus the stability of polar surfaces. These results are helpful for further understanding the polar facet-related stabilization mechanisms in oxide nanomaterials.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"40 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252041","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}