Chemphyschem最新文献_第6页

Data-Efficient Active Learning for Thermodynamic Integration: Acidity Constants of BiVO₄ in Water. 热力学整合的数据高效主动学习：水中 BiVO4 的酸度常数。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-01-02 Epub Date: 2024-11-19 DOI: 10.1002/cphc.202400490

Philipp Schienbein, Jochen Blumberger

{"title":"Data-Efficient Active Learning for Thermodynamic Integration: Acidity Constants of BiVO4 in Water.","authors":"Philipp Schienbein, Jochen Blumberger","doi":"10.1002/cphc.202400490","DOIUrl":"10.1002/cphc.202400490","url":null,"abstract":"The protonation state of molecules and surfaces is pivotal in various disciplines, including (electro-)catalysis, geochemistry, biochemistry, and pharmaceutics. Accurately and efficiently determining acidity constants is critical yet challenging, particularly when explicitly considering the electronic structure, thermal fluctuations, anharmonic vibrations, and solvation effects. In this research, we employ thermodynamic integration accelerated by committee Neural Network potentials, training a single machine learning model that accurately describes the relevant protonated, deprotonated, and intermediate states. We investigate two deprotonation reactions at the BiVO4 (010)-water interface, a promising candidate for efficient photocatalytic water splitting. Our results illustrate the convergence of the required ensemble averages over simulation time and of the final acidity constant as a function of the Kirkwood coupling parameter. We demonstrate that simulation times on the order of nanoseconds are required for statistical convergence. This time scale is currently unachievable with explicit ab-initio molecular dynamics simulations at the hybrid DFT level of theory. In contrast, our machine learning workflow only requires a few hundred DFT single point calculations for training and testing. Exploiting the extended time scales accessible, we furthermore asses the effect of commonly applied bias potentials. Thus, our study significantly advances calculating free energy differences with ab-initio accuracy.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400490"},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142375208","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}

引用次数: 0

Photoinduced Anisotropy in Thin Films of Azobenzene-Containing Liquid Crystalline Supramolecular Complexes of Various Polymer Architecture. 各种聚合物结构的含偶氮苯液晶超分子复合物薄膜的光诱导各向异性。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-01-02 Epub Date: 2024-11-05 DOI: 10.1002/cphc.202400677

Miron Bugakov, Valery Shibaev, Natalia Boiko

{"title":"Photoinduced Anisotropy in Thin Films of Azobenzene-Containing Liquid Crystalline Supramolecular Complexes of Various Polymer Architecture.","authors":"Miron Bugakov, Valery Shibaev, Natalia Boiko","doi":"10.1002/cphc.202400677","DOIUrl":"10.1002/cphc.202400677","url":null,"abstract":"Light patternable colorless liquid crystalline (LC) polymers are promising materials for functional photonic devices with broad applications in optical communication, diffractive optics, and displays. This work reports photoinduced optical anisotropy in thin films of azobenzene-containing (Azo) LC block copolymer supramolecular complexes, which can be decolorized after light patterning providing colorless patterned birefringent polymer films. The supramolecular complexes are prepared via intermolecular pyridine-phenol hydrogen bonding between a low-molecular-weight Azo phenol and host LC AB diblock and ABA triblock copolymers consisted of LC phenylbenzoate (PhM) blocks and poly(vinylpyridine) units. The molecular architecture of the host polymers and the morphological pattern formed by the complexes can affect orientational behavior of Azo groups under irradiation with linearly polarized light. Photoorientation of hydrogen-bonded Azo groups is accompanied by the cooperative orientation of non-photochromic PhM units, which form individual microphases and stabilize the orientation of Azo groups. This effect is specific for block copolymer complexes and it is absent for random copolymer complex, which is used as a reference sample. Optical anisotropy induced in films of the block copolymer complexes can be amplified by heating above the glass transition temperature and subsequent rinsing with diethyl ether allows colorless birefringent polymer films to be prepared.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400677"},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142280983","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}

引用次数: 0

Operando Spectroscopic Investigation of the Re₂O₇.2H₂O Adduct obtained by Controlled Hydration of Re₂O₇. 对 Re2O7 受控水合得到的 Re2O7.2H2O 加合物进行操作性光谱研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-01-02 Epub Date: 2024-11-20 DOI: 10.1002/cphc.202400432

Xavier Sécordel, Shreya Nandi, Asma Tougerti, Sylvain Cristol, Jean-François Paul, Valérie Briois, Camille La Fontaine, Elise Berrier

引用次数: 0

Kinetics and Dynamics of Cyclopentanone Thermal Decomposition in Gas Phase. 环戊酮在气相中的热分解动力学和动力学。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-01-02 Epub Date: 2024-11-08 DOI: 10.1002/cphc.202400825

Himani Priya, Ripan Halder, Manikandan Paranjothy

{"title":"Kinetics and Dynamics of Cyclopentanone Thermal Decomposition in Gas Phase.","authors":"Himani Priya, Ripan Halder, Manikandan Paranjothy","doi":"10.1002/cphc.202400825","DOIUrl":"10.1002/cphc.202400825","url":null,"abstract":"Cyclopentanone is a potential bio-fuel which can be produced from bio-mass. Its gas phase dissociation chemistry has attracted several experimental and theoretical investigations. In the photochemical and thermal decomposition studies of cyclopentanone, ethylene and carbon monoxide were found to be dominant reaction products along with several other compounds in smaller quantities. For the formation of ethylene and carbon monoxide, a concerted mechanism has been proposed as the primary reaction pathway. In addition, a step-wise mechanism involving ring-opened radical intermediate has also been considered. The present work reports gas phase thermal decomposition of cyclopentanone at high temperatures investigated using electronic structure theory methods, Rice-Ramsperger-Kassel-Marcus (RRKM) rate constant calculations, and Born-Oppenheimer direct classical trajectory simulations. The trajectory calculations were performed on density functional PBE96/6-31+G* potential energy surface using initial conditions selected from fixed energy normal mode distributions. Simulations showed that ethylene and carbon monoxide formed primarily via the concerted mechanism confirming the earlier predictions. In addition, step-wise pathways were also observed for the same products in lower fraction of trajectories. Furthermore, several other reaction products in smaller quantities and new mechanistic pathways were observed. The computed RRKM rate constants and simulation data are in agreement with experimental results and detailed atomic level dissociation mechanisms presented.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400825"},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142342511","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}

引用次数: 0

Synthesis and Spectroscopic Properties of Diarylethene-Subporphyrinoid Hybrids. 二元噻吩-次孢吡啶杂化物的合成与光谱特性。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-01-02 Epub Date: 2024-11-05 DOI: 10.1002/cphc.202400615

Taichi Muto, Nanari Tamiya, Akuto Takagi, Tadashi Mizutani, Didier Bourissou, Gwénaël Rapenne, Mihoko Yamada, Tsuyoshi Kawai

引用次数: 0

Stretch-Induced Ordering of Prochiral Dimethyl Sulfoxide in Anisotropic Hydrogels Analysed by ¹H and ²H Nuclear Magnetic Resonance. 通过 1H 和 2H 核磁共振分析手性二甲基亚砜在各向异性水凝胶中的拉伸有序性。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-01-02 Epub Date: 2024-11-27 DOI: 10.1002/cphc.202400731

Stuart J Elliott, Philip W Kuchel, Thomas R Eykyn

{"title":"Stretch-Induced Ordering of Prochiral Dimethyl Sulfoxide in Anisotropic Hydrogels Analysed by 1H and 2H Nuclear Magnetic Resonance.","authors":"Stuart J Elliott, Philip W Kuchel, Thomas R Eykyn","doi":"10.1002/cphc.202400731","DOIUrl":"10.1002/cphc.202400731","url":null,"abstract":"Nuclear spins in small molecules dissolved in stretched hydrogels typically have population-averaged residual interactions. The nuclear magnetic resonance (NMR) spectra of these systems often show additional peaks and splittings compared with free solutions. Residual dipolar couplings (RDCs) and quadrupolar couplings (RQCs) are observed for guest 1H and 2H nuclear spins, respectively. Dimethyl sulfoxide (DMSO) is an exquisitely sensitive probe of such biologically relevant environments since it is prochiral and becomes effectively chiral when embedded in anisotropic gelatin-based hydrogels. Measured 1H RDCs and 2H RQCs were used to estimate bond order parameters over a wide range of stretching extents. At the largest extent of stretching, the 2H splittings were -73.0 and -9.4 Hz, similar to those found for guest molecules in liquid crystals. Inhomogeneous line broadening of the 2H resonances was related to the size of the RQC due to a spatial distribution of RQCs, which was revealed using a one-dimensional slice selective imaging experiment along the stretching direction. 1H NMR spectra exhibited homogeneous line broadening, with resonance integrals that indicated concealed multiplet structure. Understanding molecular bond ordering in mechanically oriented environments provides a conceptual framework for investigating more complex systems including zeolites and those found in vivo.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400731"},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11747584/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142388392","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}

引用次数: 0

Gradient-Doped BiVO₄ Dual Photoanodes for Highly Efficient Photoelectrochemical Water Splitting. 用于高效光电化学水分离的梯度掺杂 BiVO4 双光电阳极

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-01-02 Epub Date: 2024-11-12 DOI: 10.1002/cphc.202400692

Xuhao Yang, Shuang Liang, Jiaming Miao, Yilong Yang, sKan Zhang

引用次数: 0

Se-Doping on Co₄S₃ Cathode Based on Soft Anion Chemistry to Enhance Magnesium Storage Performance. 基于软阴离子化学的 Co4S3 阴极掺杂硒以提高镁的储存性能

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-01-02 Epub Date: 2024-11-08 DOI: 10.1002/cphc.202400821

Chenkai Hu, Haifeng Ying, Wenwei Zhang, Feiyang Chao, Dongyao Zhu, Shaohua Zhu, Qinyou An

引用次数: 0

On the Solvation Properties of Menthol-Thymol Mixtures. A Molecular Dynamics Investigation. 薄荷醇-百里酚混合物的溶解特性。分子动力学研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-01-02 Epub Date: 2024-11-19 DOI: 10.1002/cphc.202400768

T Dorosh, T Mangin, E Engler, R Schurhammer, A Chaumont

{"title":"On the Solvation Properties of Menthol-Thymol Mixtures. A Molecular Dynamics Investigation.","authors":"T Dorosh, T Mangin, E Engler, R Schurhammer, A Chaumont","doi":"10.1002/cphc.202400768","DOIUrl":"10.1002/cphc.202400768","url":null,"abstract":"Using classical molecular dynamics, we have investigated the solvation of catechol, resorcinol, hydroquinone and 1,4-benzoquinone at infinite dilution, in a series of menthol - thymol mixtures in which the molar fraction of thymol (xTHY) has been increased by steps of 0.1, from 0 (pure menthol) to 1 (pure thymol). The evolution of the solvation shell around the solutes reveals that when xTHY is increased, the average number of hydrogen bonds (HB) where the solute acts as HB acceptor (HBA) and the solvent as HB donor (HBD) increases, while the amount of HB, in which the solute acts as HBD and the solvent as HBA, decreases. Overall, the total number of HBs between the different benzenediols and the solvent decreases with an increase of xTHY, while for benzoquinone the total number of HB increases. This points to the fact that \"acidic\" or HBD molecules are better solvated in mixtures with high menthol proportion, while \"basic\" or HBA molecules, are better solvated in thymol rich mixtures. The results reported herein follow the same trends as experimentally reported Kamlet-Taft parameters and present insights on how the composition of these \"deep eutectic\" mixtures maybe tweaked in order to optimize their solvation properties.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400768"},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11747588/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142342512","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}

引用次数: 0

Correlation Between Voltammetry of Immobilized Particles and Mott-Schottky Analysis of Metal Corrosion Patinas. 固定颗粒伏安法与金属腐蚀铜绿的莫特-肖特基分析之间的相关性。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-01-02 Epub Date: 2024-11-20 DOI: 10.1002/cphc.202400805

Marta Porcaro, Miguel Sanz-Abad, Laura Michetti, Alessandro Conti, Caterina De Vito, María Teresa Doménech-Carbó, Antonio Doménech-Carbó

引用次数: 0