Physical Chemistry Chemical Physics最新文献

{"title":"Expanded ensemble predictions of toluene–water partition coefficients in the SAMPL9 LogP challenge","authors":"Steven Goold, Robert M. Raddi, Vincent Voelz","doi":"10.1039/d4cp03621b","DOIUrl":"https://doi.org/10.1039/d4cp03621b","url":null,"abstract":"The logarithm of the partition coefficient (logP) between water and a nonpolar solvent is useful for characterizing a small molecule's hydrophobicity. For example, the water–octanol logP is often used as a predictor of a drug’s lipophilicity and/or membrane permeability, good indicators of its bioavailability. Existing computational predictors of water–octanol logP are generally very accurate due to the wealth of experimental measurements, but may be less so for other non-polar solvents such as toluene. In this work, we participate in a Statistical Assessment of the Modeling of Proteins and Ligands (SAMPL) logP challenge to examine the accuracy of a molecular simulation-based absolute free energy approach to predict water–toluene logP in a blind test for sixteen drug-like compounds with acid-base properties. Our simulation workflow used the OpenFF 2.0.0 force field, and an expanded ensemble (EE) method for free energy estimation, which enables efficient parallelization over multiple distributed computing clients for enhanced sampling. The EE method uses Wang-Landau flat-histogram sampling to estimate the free energy of decoupling in each solvent, and can be performed in a single simulation. Our protocol also includes a step to optimize the schedule of alchemical intermediates in each decoupling. The results show that our EE workflow is able to accurately predict free energies of transfer, achieving an RMSD of 2.26 kcal/mol, and <em>R</em><small>²</small> of 0.80. An examination of outliers suggests that improved force field parameters could achieve better accuracy. Overall, our results suggest that expanded ensemble free energy calculations provide accurate first-principles logP prediction.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"16 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462601","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":"High energy electron beam irradiation on the electrolyte enables fast-charging of lithium metal battery with long-term cycling stability","authors":"Miaomiao Yu, Qiaoan Liu, Yuxin Rao, Huasong Wang, Pengfei Liu, Xue Li, Yan Zhang, Shan Fang","doi":"10.1039/d5cp00021a","DOIUrl":"https://doi.org/10.1039/d5cp00021a","url":null,"abstract":"Electron beam (E-beam) irradiation serves as a pivotal tool within the realms of materials science, nanotechnology, and microelectronics. Its application is instrumental in altering the physical and chemical properties of materials, which enabling the exploration of material characteristics and fosters the advent of novel technologies advancements. In this work, to investigate the effect of E-beam irradiation on the electrolyte of lithium-metal batteries, a commercially available carbonate based electrolyte LB-085 was exposed to E-beam irradiation at different doses (10, 25, 50 kGy), significantly alters the chemical composition of the electrolyte and modifies various physical parameters. It effectively mitigates interfacial side reactions that occur during the cycles of an electrode, securing a stable solid state electrolyte interphase (SEI) characterized by high ionic conductivity. This, in turn, facilitates rapid charging performance of the battery. The lithium metal full-cell assembled with LiNi0.91Co0.06Mn0.03O2 (NCM91 ) demonstrates superior capacity retention, exceeded 80% after 450 cycles 4C rate and after 600 cycles at 6C rate with an irradiation dose of 50 kGy on the electrolyte. This research pioneers fresh perspectives for electrolyte optimization, focusing on enhancing the rapid charging performance of batteries.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443848","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":"Assessing residual stress generation and entrapment in glass-to-metal seals: Role of glass solidification during the cooling process","authors":"Keqian Gong, Chao Zhou, Zheng Liu, Zifeng Song, Zhangjing Shi, Weisong Zhou, Yong Zhang","doi":"10.1039/d4cp03661a","DOIUrl":"https://doi.org/10.1039/d4cp03661a","url":null,"abstract":"Glass-to-metal (GTM) seals present significant challenges due to residual stress (RS) in engineering applications. While previous studies have focused primarily on analyzing the final RS distribution, this work uniquely explores the formation and entrapment of stress during the cooling process, which has been largely overlooked. By investigating cooling-induced changes in glass properties, it reveals the pivotal role of glass solidification and the intricate interplay between thermal dynamics and mechanical properties in shaping stress distribution within GTM seals. Using a combination of photoluminescence spectroscopy and layer-by-layer polish grinding methods, five distinct solidification zones were identified and investigated: primary, secondary, bottom interference, top interference, and final. These zones exhibit different stress profiles because of the disparities in solidification rates and glass transitions, which are affected by the thermal properties of the contacting materials and their heat transfer dynamics. A notable observation from the analysis of the stress distribution along z-axis is the near absence of stress at the bottom layer, which is accompanied by minor tensile stress at the glass-metal interface. In contrast, the middle layers display a non-uniform stress distribution within the xy-plane, with stress levels intensifying proximate to the glass-metal interfaces, indicating complex stress states within these regions. The uppermost layer exhibits a complex stress profile characterized by compressive and tensile strains that attain stable equilibrium without experiencing localized peaks near the glass-metal interfaces. This research comprehensively analyzes RS formation and entrapment in GTM seals, highlighting the importance of precise thermal management during cooling to achieve desired high-performance seals.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"13 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443850","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":"Development of a Force Field for ATP – How Charge Scaling Controls Self Association","authors":"Tuan Minh Do, Nobuyuki Matubayasi, Dominik Horinek","doi":"10.1039/d4cp04270k","DOIUrl":"https://doi.org/10.1039/d4cp04270k","url":null,"abstract":"The discovery that ATP can prevent the aggregation of proteins and enhance their stability sparked significant interest in understanding the interactions between ATP and proteins. All-atom molecular dynamics simulations provide detailed insight into the underlying mechanism, while an appropriate force field must be developed. Existing force fields accurately describe the conformations of polyphosphates, but are not suitable for simulations at high ATP concentrations, because excessive self-aggregation occurs. We address this issue by scaling the atomic charges of the ATP anion and its counterions. The experimentally observed aggregation can be reproduced by using a scaling factor of 0.7 applied to the phosphate moiety of ATP and its counter ions. This charge scaling is in line with a physically motivated implicit account of polarization effects that sees increasing applications for simulations of ionic systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"42 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443852","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":"Correction: Accelerated lithium-ion diffusion via a ligand ‘hopping’ mechanism in lithium enriched solvate ionic liquids","authors":"Timothy Harte, Bhagya Dharmasiri, Garima S. Dobhal, Tiffany R. Walsh, Luke C. Henderson","doi":"10.1039/d4cp90177k","DOIUrl":"https://doi.org/10.1039/d4cp90177k","url":null,"abstract":"Correction for ‘Accelerated lithium-ion diffusion <em>via</em> a ligand ‘hopping’ mechanism in lithium enriched solvate ionic liquids’ by Timothy Harte <em>et al.</em>, <em>Phys. Chem. Chem. Phys.</em>, 2023, <strong>25</strong>, 29614–29623, https://doi.org/10.1039/D3CP04666D.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"14 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443849","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":"Estimating Advancing and Receding Contact Angles for Pure and Mixed Liquids on Smooth Solid Surfaces using PCP-SAFT Equation of State","authors":"Aliakbar Roosta, Sohrab Zendehboudi, Nima Rezaei","doi":"10.1039/d4cp04054f","DOIUrl":"https://doi.org/10.1039/d4cp04054f","url":null,"abstract":"Contact angle is an important measure of wetting in systems involving liquid-solid interfaces. This study focuses on estimating advancing and receding contact angles of pure and mixed liquids on smooth solid surfaces using perturbed-chain polar statistical associating fluid theory equation of state (PCP-SAFT EoS). For the receding contact angle, we propose a model in which the surface energy of solid containing a liquid film is approximated by the geometrical average of surface energies of the pure solid and liquid. The PCP-SAFT model is used to calculate the ratio of dispersion-to-total surface energy for diverse pure and mixed liquids. The results are validated against 104 experimental data points for advancing and receding contact angles, showing an average absolute relative deviation (AARD) of 7.4% for advancing angles and 10.6% for receding angles. In the contact angle models, there is an α-parameter in power term which is 0.75 and 0.5 for the advancing and receding contact angles, respectively. To assess the reliability of this α-parameter, we varied it and optimized it using experimental data. The optimized power term was found to be 0.74 for advancing and 0.48 for receding contact angle, and the AARD values slightly reduced to 7.2% and 10.5%, respectively. The optimized model parameter values are remarkably close to those based on the model assumptions (0.75 for advancing and 0.5 for receding), which validates the assumed values. The contact angle model combined with the PCP-SAFT framework allowed to accurately predict the advancing and receding contact angles of binary mixtures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"81 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462604","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":"Nano-wire Spin Hall Oscillator Fabricated by Novel Side-wall Transfer Lithography","authors":"Jialin Shi, Chenglong Zhang, Zhenhu Jin, Jiamin Chen","doi":"10.1039/d5cp00447k","DOIUrl":"https://doi.org/10.1039/d5cp00447k","url":null,"abstract":"Spin Hall nano oscillators (SHNOs) have garnered significant attention in the field of spintronics in recent years, particularly for their potential in neuromorphic computing. However, their sensitive regions, often below 200 nm, present considerable challenges for fabrication. The current mainstream approach relies on electron beam lithography (EBL) to define the shapes of SHNOs. While EBL is both costly and time-consuming, making it less ideal for the large-scale development and application of SHNOs. In this paper, we propose a novel fabrication method for nano-wire SHNOs using sidewall transfer lithography. This approach offers a practical solution to enhance fabrication efficiency while simultaneously reducing production costs, making it more suitable for mass production. Through experimental demonstrations, we validate the feasibility of this method and provide detailed insights into the sidewall transfer lithography process. Our findings suggest that this technique achieves higher theoretical accuracy than current fabrication methods, offering a cost-effective pathway for realizing large-scale arrays of SHNOs and promoting their application in advanced computing technologies.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"22 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444004","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":"Framework for designing main-group single-molecule magnets","authors":"Akseli Mansikkamäki, Anand Chekkottu Parambil","doi":"10.1039/d4cp04790g","DOIUrl":"https://doi.org/10.1039/d4cp04790g","url":null,"abstract":"Single-molecule magnets (SMMs) are molecular entities with strongly anisotropic magnetic moment. As a result, SMMs display slow relaxation of magnetization at the macroscopic scale. Up to date all experimentally characterized SMMs are based on either d- or f-block metals with lanthanides proving to be the most successful. In the present work, a framework for constructing SMMs consisting purely of main-group elements will be outlined by computational and theoretical means. The proposed main-group SMMs utilize the strong spin-orbit coupling of a single heavy p-block atom or ion that can lead to strong magnetic anisotropy and pronounced SMM properties. A theoretical crystal-field model is developed to describe the magnetic properties of p-block SMMs with a minimal set of parameters related to the chemical structure of the SMMs. The model is used to establish which p-block elements and oxidation states can lead to SMM behavior. A large number of model structures are studied to establish general features of optimal chemical structures. These include one- and two-coordinate structures involving ligands with different coordination modes and all group 13 to 17 elements in periods 4 to 6. The results show that the most viable structures are based on mono-coordinated complexes of bismuth in oxidation state 0 with σ-donor ligands. Structures with bulkier ligands that sterically protect the bismuth atom are then proposed as a starting point for the practical realization of main-group SMMs. The calculations show that minimizing the anagostic interactions with the bismuth atom is essential in the ligand design, which along with the low oxidation state of bismuth introduces significant synthetic challenges The results do, however, show that main-group SMMs are plausible from a practical point of view within a limited set of heavier p-block elements in specific oxidation states. Furthermore, the proposed SMMs display much larger energy barriers for the relaxation of magnetization than even the best lanthanide-based SMMs do. This indicates that it is possible that main-group SMMs can supersede even the best currently known SMMs based on d- or f-block element","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443851","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":"Ligand-mediated interaction in a dispersion of lead-halide perovskite nanocubes: implications on directed structures in equilibrium†","authors":"Avik Sasmal, Edwine Tendong, Tanusri Saha-Dasgupta and Jaydeb Chakrabarti","doi":"10.1039/D4CP04012K","DOIUrl":"10.1039/D4CP04012K","url":null,"abstract":"<p >Motivated by the experimental reports on the formation of ordered nano-structures of ligand-dressed Cs–Pb-halide nanoparticles, employing a combination of density functional theory, molecular dynamics, metadynamics and Monte Carlo simulation techniques, we investigate the microscopic mechanism driving such structures. Our rigorous studies focused on CsPbBr<small>₃</small> nanoparticles take into account the realistic situation in terms of different synthesis conditions. In particular, Br vacancies, the neutral and charged forms of ligands, and the presence of a variety of solvents of different polarities are considered. Our work establishes the crucial role of electrostatics driving preferential matching of facets paving the way to the formation of directed structures. In particular, the importance of Br vacancies, the polarity of solvents, and the preference for slightly alkaline synthesis conditions are highlighted. The microscopic understanding thus provided will be useful in designing targeted nano-structures.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 10","pages":" 5098-5108"},"PeriodicalIF":2.9,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443853","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":"Exploring coinage bonding interactions in [Au(CN)4]− assemblies with silver and zinc complexes: a structural and theoretical study†","authors":"Alessia Giordana, Emanuele Priola, Ghodrat Mahmoudi, Esmail Doustkhah, Rosa M. Gomila, Ennio Zangrando, Eliano Diana, Lorenza Operti and Antonio Frontera","doi":"10.1039/D4CP04818K","DOIUrl":"10.1039/D4CP04818K","url":null,"abstract":"<p >This study investigates the non-covalent interactions between [Au(CN)<small>₄</small>]<small>⁻</small> anions and silver and zinc complexes, with a particular focus on coinage bonding interactions. Four new complexes, [Ag<small>₂</small>(pyNP)<small>₂</small>][Au(CN)<small>₄</small>]<small>₂</small> (<strong>1</strong>) [Zn(bipy)<small>₃</small>][Au(CN)<small>₄</small>]<small>₂</small> (<strong>2</strong>), [Zn(phen)<small>₃</small>][Au(CN)<small>₄</small>]<small>₂</small> (<strong>3</strong>) and [Zn(terpy)(H<small>₂</small>O)<small>₃</small>][Au(CN)<small>₄</small>]<small>₂</small> (<strong>4</strong>), were synthesized and spectroscopically characterized, including their X-ray solid-state structures, where pyNP is (2-(2-pyridyl)-1,8-naphthyridine, bipy is 2,2′ bipyridine, phen is 1,10′-phenantroline and terpy is terpyridine. The [Au(CN)<small>₄</small>]<small>⁻</small> anion exhibits unique anion⋯anion interactions, despite the electrostatic repulsion, forming stable 1D supramolecular polymers in the solid state. Using a combination of X-ray crystallography and DFT calculations, this work characterizes the coordination and non-covalent bonding modes, including Au⋯N coinage bonds. Energy decomposition analysis (EDA), QTAIM, and NCIplot methods were applied to understand the energetics and bonding nature. The study reveals that electrostatic and dispersion forces play critical roles in stabilizing these assemblies, especially in the formation of π-stacking and T-shaped dimers. These findings offer insights into the design of new materials leveraging coinage bonding in molecular architectures.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 10","pages":" 5395-5402"},"PeriodicalIF":2.9,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cp/d4cp04818k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462605","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}