Journal of Chemical Physics最新文献_第5页

How dynamic surface restructuring impacts intra-particle catalytic cooperativity. 动态表面重组如何影响粒子内催化合作性

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-21 DOI: 10.1063/5.0239455

Bhawakshi Punia, Srabanti Chaudhury, Anatoly Kolomeisky

{"title":"How dynamic surface restructuring impacts intra-particle catalytic cooperativity.","authors":"Bhawakshi Punia, Srabanti Chaudhury, Anatoly Kolomeisky","doi":"10.1063/5.0239455","DOIUrl":"10.1063/5.0239455","url":null,"abstract":"Recent experiments indicated that nanoparticles (NPs) might efficiently catalyze multiple chemical reactions, frequently exhibiting new phenomena. One of those surprising observations is intra-particle catalytic cooperativity, when the reactions at one active site can stimulate the reactions at spatially distant sites. Theoretical explanations of these phenomena have been presented, pointing out the important role of charged hole dynamics. However, the crucial feature of nanoparticles that can undergo dynamic structural surface rearrangements, potentially affecting the catalytic properties, has not yet been accounted for. We present a theoretical study of the effect of dynamic restructuring in NPs on intra-particle catalytic cooperativity. It is done by extending the original static discrete-state stochastic framework that quantitatively evaluates the catalytic communications. The dynamic restructuring is modeled as stochastic transitions between states with different dynamic properties of charged holes. Our analysis reveals that the communication times always decrease with increasing rates of dynamic restructuring, while the communication lengths exhibit a dynamic behavior that depends on how dynamic fluctuations affect migration and death rates of charged holes. Computer simulations fully support theoretical predictions. These findings provide important insights into the microscopic mechanisms of catalysis on single NPs, suggesting specific routes to rationally design more efficient catalytic systems.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142668170","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Critical adsorption of polyelectrolytes onto highly oppositely charged surfaces: Effects of charge renormalization. 聚电解质在高度对置电荷表面上的临界吸附：电荷重正化的影响

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-21 DOI: 10.1063/5.0238717

Felipe Arantes Africo, Andrey G Cherstvy, Sidney Jurado de Carvalho

{"title":"Critical adsorption of polyelectrolytes onto highly oppositely charged surfaces: Effects of charge renormalization.","authors":"Felipe Arantes Africo, Andrey G Cherstvy, Sidney Jurado de Carvalho","doi":"10.1063/5.0238717","DOIUrl":"https://doi.org/10.1063/5.0238717","url":null,"abstract":"The critical adsorption conditions of polyelectrolytes (PEs) onto planar, cylindrical, and spherical surfaces were obtained by solving the Edwards equation using the Wentzel-Kramers-Brillouin (WKB) method. It demonstrated to provide a suitable analytical approach for all three geometries, in conformity with some experimental results for weakly charged micelles. However, our Monte Carlo simulations implementing approximate solutions of the nonlinear Poisson-Boltzmann equation for highly charged surfaces indicated recently the emergence of a limiting value of ionic strength due to a nonlinear dependence of the electrostatic (ES) potential on the surface-charge density σ. Beyond this limiting ionic strength, the PE adsorption no longer occurs, shifting the standard paradigm. In this work, we employ the concept of a renormalized charge and use the WKB method to study the effects of this nonlinearity on the critical adsorption conditions, density profile, and adsorbed layer of PE segments, all in comparison with the results of the linear Debye-Hückel (DH) approach. Charge renormalization makes it possible to use the known WKB solutions in the DH regime also for surfaces with high σ, introducing a saturation effect observed in the nonlinear case. The larger ES screening affects the density profile and the adsorbed layer of PEs, promoting a more dispersed distribution of PEs at higher surface-charge densities. Our analytical results for the critical adsorption curve reproduce the limiting ionic strength for high σ and also recover the DH regime at low σ.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142681896","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Constructing surface oxygen vacancy in the [Bi2O2]2+ layer defects mediated Bi2MoO6 enhanced visible light responsive photocatalytic activity. 在[Bi2O2]2+层缺陷中构建表面氧空位，介导 Bi2MoO6 增强可见光响应光催化活性。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-14 DOI: 10.1063/5.0228635

Yali Zhu, Rong Wu, Aolin Li, Jialei Hui, Zhilong Zhang, Shunhang Wei

引用次数: 0

Dissipative split-charge formalism: Ohm's law, Nyquist noise, and non-contact friction. 耗散分裂电荷形式主义：欧姆定律、奈奎斯特噪声和非接触摩擦。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-14 DOI: 10.1063/5.0242185

Martin H Müser

引用次数: 0

Erratum: "A random batch Ewald method for charged particles in the isothermal-isobaric ensemble" [J. Chem. Phys. 157, 144102 (2022)]. 勘误："等温等压集合中带电粒子的随机批量埃瓦尔德方法" [J. Chem. Phys. 157, 144102 (2022)].

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-14 DOI: 10.1063/5.0245101

Jiuyang Liang, Pan Tan, Liang Hong, Shi Jin, Zhenli Xu, Lei Li

引用次数: 0

Rational design of MoS2/CNT heterostructure with rich S-vacancy for enhanced HER performance. 合理设计具有丰富 S-空位的 MoS2/CNT 异质结构，提高 HER 性能。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-14 DOI: 10.1063/5.0237254

Yuxin Sun, Jinhua Li, Zhiying Wang, Fengxue Tan, Kaixi Shi, Yingjiao Zhai

{"title":"Rational design of MoS2/CNT heterostructure with rich S-vacancy for enhanced HER performance.","authors":"Yuxin Sun, Jinhua Li, Zhiying Wang, Fengxue Tan, Kaixi Shi, Yingjiao Zhai","doi":"10.1063/5.0237254","DOIUrl":"https://doi.org/10.1063/5.0237254","url":null,"abstract":"Molybdenum disulfide (MoS2) is a promising electrocatalyst for the hydrogen evolution reaction (HER) due to excellent stability and low cost. However, the utilization in electrocatalytic hydrogen evolution is constrained by inherent shortcomings, including fewer edge active sites, poor dispersion, and electrical conductivity. In this work, MoS2 was compounded with carbon nanotubes (CNTs), which are known for their high specific surface area and excellent electrical conductivity. These CNTs, laden with oxygen-containing functional groups, provided nucleation sites that facilitated the rapid assembly of MoS2 nanoflowers under hydrothermal conditions within 3 h. Due to their diminutive size (∼300 nm), these nanoflowers possess a large specific surface area and numerous active sites at their edges. Furthermore, MoS2 nanoflowers exhibited a high concentration of intrinsic S-vacancies. This heterojunction material exhibited superior HER properties. In addition, density functional theory simulation further confirmed that the MoS2 with S vacancy and CNT heterojunction electrocatalysts (VS-M/C) provided a fast charge transfer pathway for water electrolysis, and analysis showed that the conduction band minimum and valence band maximum were mainly contributed by the d orbits of Mo and the p orbits of C. This study proffered a novel approach for the engineering of high-performance MoS2-based HER electrocatalysts.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 18","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142620513","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Isotropic ↔ anisotropic surface geometry transitions induced by adsorbed surfactants at water/vapor interfaces. 水/蒸汽界面上吸附的表面活性剂诱发的各向同性 ↔ 各向异性表面几何转换。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-14 DOI: 10.1063/5.0237563

Nitesh Kumar, Joshua Bilsky, Aurora E Clark

{"title":"Isotropic ↔ anisotropic surface geometry transitions induced by adsorbed surfactants at water/vapor interfaces.","authors":"Nitesh Kumar, Joshua Bilsky, Aurora E Clark","doi":"10.1063/5.0237563","DOIUrl":"https://doi.org/10.1063/5.0237563","url":null,"abstract":"Adsorbates at a water/vapor interface change the surface geometry through altered surface tension, yet detailed theoretical studies are relatively sparse, and many applications focus on ensemble average characteristics. Here, we demonstrate that different interpretations of surface geometry emerge when considering the distributions of surface curvature and orientation as a function of adsorbed surfactant concentration and sterics. At low surface densities, the tributyl phosphate (TBP) sorbed water/vapor surface has an increased presence of ridges that are defined by principal curvatures κ1 and κ2 of opposite signs yet close in magnitude. As the TBP surface density increases, the difference in principal curvatures slowly increases. There is a distinct transition of the surface geometry, where the ridge-like features become much more pronounced, having sides whose orientation is normal to a flat interfacial plane. Thus, as the TBP surfactant is added to the surface, the surface curvatures become anisotropic in terms of the difference in magnitude of κ1 and κ2. We label this an isotropic → anisotropic geometric transition. Comparing the surface geometry as a function of the carbon tail length of the alkyl phosphate surfactant reveals that smaller surfactants also anisotropically enhance surface curvatures and that adsorbed alkyl tails to the surface stabilize and increase the symmetry of surface waves along the two principal curvature axes. We label this an anisotropic → isotropic geometric transition. These results reflect the opportunity to incorporate more realistic distributions of surface geometry within the collective understanding of statistical theories of surfaces, including capillary wave theory.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 18","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142621410","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Slow global motions in biosolids studied by the deuteron stimulated echo NMR experiment. 通过氘核刺激回波核磁共振实验研究生物固体中的缓慢全局运动。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-14 DOI: 10.1063/5.0236042

Alexey Krushelnitsky, Farhad Shahsavan, Günter Hempel, Nail Fatkullin

{"title":"Slow global motions in biosolids studied by the deuteron stimulated echo NMR experiment.","authors":"Alexey Krushelnitsky, Farhad Shahsavan, Günter Hempel, Nail Fatkullin","doi":"10.1063/5.0236042","DOIUrl":"https://doi.org/10.1063/5.0236042","url":null,"abstract":"Recent 15N R1ρ-relaxation studies have shown that proteins in the solid state undergo slow, low amplitude global motion in the sub-millisecond time range. This range is at the edge of the time window for R1ρ experiments and, therefore, the motional parameters obtained by this method are not precise or reliable. In this paper, we present a 2H stimulated echo study of this type of molecular dynamics. The 2H stimulated echo experiments on a static sample allow for direct measurement of the correlation function in the time range of 10-6-10-1 s, making them well suited to study this type of molecular mobility. We have conducted a detailed analytical and numerical comparison of the correlation functions obtained from the relaxation and stimulated echo experiments, which are generally different. We have identified conditions and algorithms that enable a direct comparison of the relaxation and stimulated echo experimental results. Using the protein GB1 in the form of a lyophilized powder, we have demonstrated that 15N R1ρ-relaxation and 2H stimulated echo experiments yield essentially the same slow-motion correlation function. Surprisingly, this type of motion is observed not only in the protein sample but also in the tripeptide and single amino acid solid samples. The comparison of data measured in these three samples at different temperatures led us to conclude that this slow motion is, in fact, ultrasonic phonons, which seem to be inherent to all rigid biological solids.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 18","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142620842","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Selecting relevant structural features for glassy dynamics by information imbalance. 通过信息不平衡为玻璃动力学选择相关结构特征

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-14 DOI: 10.1063/5.0235084

Anand Sharma, Chen Liu, Misaki Ozawa

引用次数: 0

Rate coefficients for C and O2 reactive collisions relevant to interstellar clouds from QCT and machine learning. 通过 QCT 和机器学习获得的与星际云相关的 C 和 O2 反应碰撞的速率系数。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-14 DOI: 10.1063/5.0238311

Xia Huang, Xin-Lu Cheng, Hong Zhang

{"title":"Rate coefficients for C and O2 reactive collisions relevant to interstellar clouds from QCT and machine learning.","authors":"Xia Huang, Xin-Lu Cheng, Hong Zhang","doi":"10.1063/5.0238311","DOIUrl":"https://doi.org/10.1063/5.0238311","url":null,"abstract":"The chemical reactions between certain interstellar molecules are exothermic in nature and barrierless in the entrance channel, allowing these reactions to occur rapidly even at low astronomical temperatures, e.g., C and O2 interaction. Obtaining detailed rovibrational transition parameters for the reaction between C and O2, such as state-selected rate coefficients, is crucial for studying the associated atmospheric and astronomical environments. Hence, this work presents an approach that combines quasi-classical trajectory calculations with machine learning techniques based on Neural Network (NN) and Gaussian Process Regression (GPR) to determine state-selected rate coefficients. Employing this approach, we significantly reduced the computational requirements while simultaneously obtaining the accurate state-selected reaction cross sections and rate coefficients for the collision of C and O2. Both the NN-based and GPR-based models established in this work accurately predict the results calculated from explicit numerical calculations in the explored temperature range of 50-1500 K, achieving a coefficient of determination R2 > 0.96. Most importantly, the current work provides the most comprehensive dataset of rovibrational rate coefficients of v = 0-4, j = 0-70 → v' = 0-15 for the astrophysical modeling of the C-O2 collision system.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 18","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142604689","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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