Physical Chemistry Chemical Physics最新文献

{"title":"Circular Polarised Absorption and Emission of Exciton-Coupled Homo-Dimeric Chromophores in Anisotropic Systems","authors":"Lennart B.-Å. Johansson","doi":"10.1039/d6cp02975b","DOIUrl":"https://doi.org/10.1039/d6cp02975b","url":null,"abstract":"The present theoretical work intends to examine the influence of order, and reorientation dynamics of homo-dimeric chiral and exciton coupled chromophores in anisotropic systems.The free monomers are achiral. Various experiments are proposed, based on Circular Dichroism (CD) absorption and Circular Polarised (CP) emission, which are intended for examining properties and behaviour of chiral dimers. The particular experiments concern a dimer dissolved in macroscopic isotropic and anisotropic molecular systems. The systems could involve liquid crystals, lipid membranes, or model membranes, proteins, etc., which all are anisotropic at a molecular level. Experimental results are simulated, partly based on published data. In a wider perspective the aim is to extend the view of CP experimental applications, as well as the analysis of CD absorption and CP emission obtained on exciton coupled homo-dimeric chromophores. An approach is developed for the determination and measurement of the CP emission anisotropy. The experiments propose and combine properties of homo-dimeric chromophores for probing anisotropic environments, e.g., in life-science applications at a molecular and a cellular scale.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"37 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225823","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":"DRAGON-3D: An Electron-Density-Aware Generative Model for Dual-Target Drug Molecule Generation","authors":"Zhong-Xing Zhou,Hong-Xing Zhang,Shi Feng,Yan Zhao,Zhen-Yang Liu,Jun-Bao Huang,Qing-Chuan Zheng","doi":"10.1039/d6cp03204d","DOIUrl":"https://doi.org/10.1039/d6cp03204d","url":null,"abstract":"Dual-target drug molecule generation is a significant computational challenge due to the structural constraints imposed by two protein binding pockets. Existing generative models typically rely on scarce dual-target drug datasets and struggle to capture three-dimensional (3D) structural and physicochemical interactions between protein pockets and ligands, limiting generalization to new target pairs. To address these limitations, we propose DRAGON-3D, a general dual-target drug molecule generation model based on latent-space fusion of 3D electron-density representations of diverse target pairs. Our model employs a novel bi-Net β-VAE architecture and an innovative dualpretraining strategy, enabling dual-target molecule generation using only single-target data. By integrating 3D spatial electron-density with 2D molecular topology, DRAGON-3D enhances generalization and spatial compatibility across diverse dual-target protein pairs. Comprehensive benchmarks show that DRAGON-3D is a promising framework for the generation of candidate dual-target molecules, particularly in molecular diversity, drug-likeness (QED), deployability, generalizability, and interpretability. Overall, DRAGON-3D provides an efficient, interpretable, and electron-density-informed paradigm for de novo dual-target molecular generation.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"13 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225826","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":"Anisotropic Electron Inelastic Scattering and Monte Carlo Simulation of Electron Emission from Graphite","authors":"Zhenhuan Min,Shifeng Mao,Zejun Ding","doi":"10.1039/d6cp02976k","DOIUrl":"https://doi.org/10.1039/d6cp02976k","url":null,"abstract":"We develop a dielectric-functional formulation of anisotropic electron inelastic scattering and an anisotropic Monte Carlo (MC) model for electron transport in uniaxial materials. Within a tensorial dielectric-response framework, the inelastic scattering probability is expressed as a triple differential cross section in a crystal-fixed coordinate system. For a uniaxial crystal with parallel and perpendicular dielectric-function components, an explicit analytical expression is derived without invoking the small-angle approximation. The corresponding double differential cross section, single differential energy-loss distribution, and inelastic mean free path (IMFP) are obtained by numerical integration, all depending on the electron-velocity orientation relative to the crystal axis. The anisotropic differential inverse IMFP is implemented in MC simulations down to the low-energy cascade-secondary-electron region ， which enables the calculation of electron emission yields for graphite. No statistically meaningful difference is found in secondary electron yield or backscattering coefficient for normal incidence on graphite basal-and edge-plane surfaces. This supports the hypothesis that multiple scattering, especially large-angle elastic scattering, smooths the weak directional dependence of anisotropic inelastic scattering.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225825","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 Analysis of Magnetic Superexchange in Cubic Fluoro- and Oxo-perovskites","authors":"Inés Sánchez-Movellán,Richard Dronskowski,Ángel Martín Pendás,Pablo Garcia Fernandez,Miguel Moreno,Jose Antonio Aramburu","doi":"10.1039/d6cp03094g","DOIUrl":"https://doi.org/10.1039/d6cp03094g","url":null,"abstract":"We present a comprehensive first-principles analysis of magnetic ordering via superexchange in KMnF₃, CaMnO₃, and SrMnO₃, which constitutes an extension of our previous study on fluorides KNiF₃ and KVF₃. Using the metallic non-magnetic (NM) phase as a reference, we examine the Mott transition to the insulating Antiferromagnetic (AFM) phase from first principles calculations and compare it with the predictions of the Hubbard model, which only considers the antibonding magnetic orbitals. We show that spin-polarization promotes the charge transfer between atoms, localizing the spin density on each site and opening a gap at the Fermi level. The microscopic mechanism driving this transition, however, differs among the systems. A detailed analysis on energy contributions, charge redistribution and metal-ligand bonding reveals significant differences between divalent transition metal cations in fluorides and Mn4+ in oxides, due to the enhanced covalency in the latter. Despite these differences, a unifying, bonding-driven mechanism for AFM stabilization emerges: in all compounds, the energy gain relative to the FM phase arises from a slightly greater delocalization of minority-spin electrons associated with deep bonding ligand orbitals. This subtle redistribution strengthens the key role played by chemical bond in superexchange interactions and leads to a small but systematic kinetic-energy gain. Our findings highlight the limitations of canonical minimal-basis models that neglect deep bonding orbitals and charge transfer, and demonstrate the need for quantitative first-principles approaches to accurately describe magnetism in transition-metal perovskites.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"3 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225804","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":"Prediction of global Raman spectral features in minerals from structure and composition","authors":"Zhao Liu,Yihao Chen,Chunguang Dong,Meijie Zhang","doi":"10.1039/d6cp03858a","DOIUrl":"https://doi.org/10.1039/d6cp03858a","url":null,"abstract":"How well structure and composition predict the global features of mineral Raman spectra remains unclear. Using 1,842 quality-controlled RRUFF spectra, 11 spectral endpoints and five descriptor classes, we evaluated formula-grouped predictive models. The full model achieved out-of-fold R² of 0.38–0.44 for peak count, spectral centroid and skewness, and 0.26 for mean linewidth. Relative to a chemical-family and crystal-system baseline, the descriptors improved prediction for 9 of 11 endpoints, most strongly for mean linewidth (ΔR² = +0.24). Group-theoretical Raman-active mode count was only weakly associated with observed peak count (Spearman ρ = 0.33), and leave-one-family-out validation showed substantial losses in transfer performance. These results quantify both the predictive content and the extrapolation limits of static structure- and composition-derived descriptors.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"75 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225805","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":"NAP-PES and DFT to disentangle water adsorption on γ-FeO versus α-FeO","authors":"Saida Mtakham,Antoine Barbier,Helene Magnan,Mathieu Silly,Bruno Domenichini,Celine Dupont","doi":"10.1039/d6cp03587f","DOIUrl":"https://doi.org/10.1039/d6cp03587f","url":null,"abstract":"The interaction of water with maghemite is investigated thanks to Near Ambient Pressure -PhotoEmission Spectroscopy (NAP-PES) experiments combined with Density Functional Theory (DFT) calculations. PES experiments lead to O 1s spectra with a different shape and in particular noticeably broader compared to those measured on hematite. DFT calculations demonstrate a larger amount and a wider diversity for water adsorption on γ-Fe 2 O 3 (111) compared to α-Fe 2 O 3 (0001). This diversity can be directly related to the roughness of the maghemite surface which is significantly different from the highly smooth and symetric surface of hematite. To go further, PES spectra of both maghemite and hematite surfaces are modeled through the method developed by Köhler et al. 1 in presence of adsorbed water. Obtained results are fully consistent with experimental ones, allowing to explain the differences of behavior between the two oxides.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"52 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225815","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":"Shift in binding site preference during oxygen adsorption on Au(111) at higher coverages and its impact on the thermodynamic phase diagram","authors":"Pranali Chavan,E. V. Charan Reddy,Abhijit Chatterjee","doi":"10.1039/d6cp02886a","DOIUrl":"https://doi.org/10.1039/d6cp02886a","url":null,"abstract":"Adsorbed oxygen plays a critical role in gold catalysis and it participates as an active species in many industrial reactions. We explore the oxygen adlayer phases on gold as a function of coverage and temperature in this work. The phase diagram of O/Au(111) is determined using cluster expansion based kinetic Monte Carlo (KMC) simulations over a coverage range of 0.05–0.45 ML for conditions relevant to room temperature catalysis. Both fcc and hcp adsorption sites are considered in our calculations. The KMC simulations reveal the coexistence of three ordered surface phases, namely, p(√7 × √7)R19.1°, p(2 × 2) and p(√3 × √3)R30°-2O at temperatures of 200–400 K. Although fcc sites are preferred at low O coverages, hcp sites can also become favorable at higher coverage. This study improves our understanding of the local oxygen arrangements on the Au(111) surface, and provides a theoretical basis for identifying reactive O sites for catalytic reactions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"8 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225831","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":"Tuning of Second-order Nonlinear Optical Response of 𝐶60- and 𝐶70-triphenylamine-BODIPY Triads","authors":"Anushree Dutta,Subhash Chandra Makhal,Rucha Vaijanath Gitte,Ramprasad Misra,Rudraditya Sarkar,Nabanita Deb","doi":"10.1039/d6cp02291j","DOIUrl":"https://doi.org/10.1039/d6cp02291j","url":null,"abstract":"Optimization of the electronic donor (D) and acceptor (A) strength, 𝜋-conjugation and the surrounding medium of an intramolecular charge transfer (ICT)-based molecule could result in red-shifted absorption maxima as well as enhancement of its second-order nonlinear optical (NLO) response. Here, we present a comprehensive investigation into the origin of the first hyperpolarizability (𝛽) of novel 𝐶60-BODIPY-Bis-triphenylamine (𝐶60-BODIPY-TPA) and 𝐶70-BODIPY-Bis-triphenylamine (𝐶70-BODIPY-TPA) triads by systematically varying the linker units and peripheral D/A substitutions, as well as analyzing the solvent effects influencing the 𝛽 of the studied molecules. The calculations are performed on the global minimum geometry obtained using Global Optimizer Algorithm (GOAT) protocol that account for the structural flexibility of some of the studied chromophores. Calculations using density functional theory (DFT) employing the long-range corrected CAM-B3LYP functional revealed that changes in electron-donating/withdrawing groups and 𝜋-conjugated linkers modulate the charge delocalization, resulting in significantly altered 𝛽 values. Solvent environment further influences these effects through differential stabilization of charge-separated excited states. The Hyper–Rayleigh Scattering first hyperpolarizability (𝛽HRS) with 1064 nm excitation are computed in the gas phase, toluene, and acetonitrile. Analyses of dipolar and octupolar contributions, as well as depolarization ratios, provide further insight into the charge transfer nature of the studied molecules. While replacement of the 𝐶70 unit by 𝐶60 in 𝐶70-BODIPY-TPA led to enhancement of the 𝛽HRS value, replacing the 𝐶60 with either non-fullerene acceptor -𝑁𝑂2 or pyrrole in 𝐶60-BODIPYTPA gives rise to higher 𝛽HRS, indicating optimization of parameters governing charge transfer could lead to higher NLO response. The results presented could provide guidelines for the rational design of efficient BODIPY-based molecular triads for photonic applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"56 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225833","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 spectra of lanthanide oxide clusters: Prevalence and importance of shake-up transitions","authors":"Lee Michael Thompson,Hrant P. Hratchian,Caroline Jarrold","doi":"10.1039/d6cp01491g","DOIUrl":"https://doi.org/10.1039/d6cp01491g","url":null,"abstract":"Lanthanides are ubiquitous in technologies used in daily life. The properties of lanthanide-based bulk and nanoscale materials are governed by the unique electronic structures of the lanthanide atoms, which are readily probed via atomic and small-molecule spectroscopy. In this perspective, we introduce an accessible framework for understanding the electronic structures of lanthanide molecules. We then focus on photodetachment spectroscopies, which provide rich molecular and electronic structural information for both anion and neutral charge states. Efforts to map the electronic structures of neutrals using photodetachment of negative ions is further enriched by the effects of strong photoelectron-valence electron interactions, uniquely pronounced in lanthanide-based molecular systems, that drive multi-electron shake-up transitions. We additionally explore some of the computational and theoretical challenges and opportunities arising in this chemical-physical space, including how the kinetic energy of the ejected electron can influence the final shake-up state populations. Results hold the promise to inform development of exciting new applications in a range of technologies.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225894","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":"Direct observation of opposite migration of photo-generated electrons and holes along the [001] direction in wurtzite ZnO","authors":"Xiao Du,Rujia Xie,Qi Luo,Jiaoyang Qu,Zhaotie Liu,Bin Liu,Heqing Yang","doi":"10.1039/d6cp01712f","DOIUrl":"https://doi.org/10.1039/d6cp01712f","url":null,"abstract":"To date, the mechanism of photogenerated charge separation in photocatalysts remains unclear, and there is no atomic scale structural model to guide the synthesis of photocatalysts. To demonstrate the polar superstructure photocatalytic model, here, we use the polar [0001] direction of wurtzite ZnO as a model to study the separation of photogenerated charges along the polar direction. We observed diode rectification, spontaneous voltage, directional electron migration, photovoltage, and photocurrent along the polar [0001] direction. The rectification ratio and spontaneous voltage were 54 ± 4 and 34.8 ± 2.4 mV, respectively. At a light power density of 0.120 W cm−2, the photocurrent and photovoltage were 46.6 ± 1.4 nA and 20.0 ± 1.0 mV, respectively. However, none of these phenomena are observed along the non-polar [12̄\"10] direction perpendicular to [0001]. Moreover, along the [0001] direction, the migration of photogenerated electrons and the subsequent reverse migration of holes are observed. All these observations indicate the existence of spontaneous electric field (Es) in the [0001] polar direction of ZnO. The Es drives the directional migration of electrons and photogenerated electrons, and thus these phenomena occur in the [0001] direction. These findings offer conclusive evidence supporting the polar superstructure photocatalytic model. This photocatalytic model not only contributes to the understanding of morphology- and crystal facet-dependent photocatalytic properties as well as facet-selective photodeposition but also enables the atomic-scale design and synthesis of highly efficient photocatalysts.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"2 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225837","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}