Chemical physics reviews最新文献

Quantum theory of stimulated Raman scattering microscopy. 受激拉曼散射显微镜的量子理论。

IF 6.2 Q2 CHEMISTRY, PHYSICAL

Chemical physics reviews

Pub Date : 2025-06-01 Epub Date: 2025-05-27 DOI: 10.1063/5.0248085

Xin Gao, Wei Min

Since its advent 17 years ago, stimulated Raman scattering (SRS) microscopy has emerged as a transformative imaging modality by visualizing chemical bonds with high sensitivity, speed, specificity, and resolution. Despite its enormous success, a rigorous theory is yet lacking in the community. The fundamental question of just why and how much SRS microscopy can outperform conventional Raman microscopy has not been quantitatively answered. Raman scattering, traditionally understood through the Raman cross section (σ_Raman), has long been believed weak due to its extremely small values when compared to linear absorption cross sections. However, this view is incomplete and even misleading since Raman scattering and linear absorption processes involve different orders of light-matter interaction. In this review, we summarize the recently developed stimulated response formulation, which defines the stimulated Raman cross section (σ_SRS) in the same spirit of Einstein's B coefficient. Unlike σ_Raman, σ_SRS turns out to be intrinsically strong and even exceeding the electronic counterparts, which is supported by experimental measurements and quantum electrodynamic theories. This new framework reveals a previously unknown duality nature of Raman scattering, where both σ_Raman and σ_SRS can exhibit vastly different magnitudes for the same molecule, connected by the influence of vacuum zero-point fluctuations. Additionally, the Raman duality also generalizes Einstein's coefficients so that four processes (spontaneous and stimulated emission, spontaneous Raman and SRS) are unified. Finally, the formulation provides quantitative prediction of the absolute signal and detectability of SRS microscopy. We can prove that SRS excels in high spatiotemporal regimes, explaining its unparalleled ability to image chemical bonds, which inherently demand high spatial and temporal resolution. We expect this theory to facilitate both scientific understanding and technological applications of Raman spectroscopy.

自17年前问世以来，受激拉曼散射（SRS）显微镜已经成为一种变革性的成像方式，通过高灵敏度、高速度、高特异性和高分辨率的化学键可视化。尽管它取得了巨大的成功，但在社区中仍缺乏严谨的理论。SRS显微镜为什么以及在多大程度上优于传统的拉曼显微镜的基本问题还没有得到定量的回答。拉曼散射，传统上通过拉曼截面（σ拉曼）来理解，长期以来被认为是弱的，因为与线性吸收截面相比，它的值非常小。然而，这种观点是不完整的，甚至是误导性的，因为拉曼散射和线性吸收过程涉及不同阶次的光-物质相互作用。在本文中，我们总结了最近发展的受激响应公式，该公式与爱因斯坦的B系数相同，定义了受激拉曼截面（σSRS）。与σ拉曼不同，σSRS在本质上是强的，甚至超过了电子拉曼，这得到了实验测量和量子电动力学理论的支持。这个新的框架揭示了拉曼散射的一个以前未知的对偶性质，其中σ拉曼和σSRS在同一分子中可以表现出截然不同的量级，由真空零点波动的影响连接起来。此外，拉曼对偶性还概括了爱因斯坦的系数，使四个过程（自发和受激发射、自发拉曼和SRS）统一起来。最后，该公式提供了SRS显微镜绝对信号和可检测性的定量预测。我们可以证明SRS在高时空状态下表现出色，这解释了其无与伦比的化学键成像能力，而化学键本身就需要高空间和时间分辨率。我们期望这一理论能促进对拉曼光谱的科学认识和技术应用。

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引用次数: 0

Rational engineering of semiconductor-based photoanodes for photoelectrochemical cathodic protection 用于光电化学阴极保护的半导体光阳极的合理工程设计

Q2 CHEMISTRY, PHYSICAL

Chemical physics reviews

Pub Date : 2024-01-10 DOI: 10.1063/5.0183558

Xiangyan Chen, Shaopeng Wang, Shaohua Shen

Photoelectrochemical (PEC) cathodic protection based on semiconductor photoanodes, by combining solar energy utilization and metal anticorrosion, provides a promising platform for developing an environmentally friendly metal protection technology. In this context, semiconductors (e.g., TiO2, ZnO, SrTiO3, BiVO4, and g-C3N4), with merits of suitable band structure, good chemical stability, and low cost, have attracted extensive attention among the investigated photoanode candidates. However, the poor optical absorption properties and the high photogenerated charge recombination rate severely limit their photocathodic protection performances. In order to break these limitations, different modification strategies for these photoanodes have been developed toward the significant enhancement in PEC cathodic protection properties. In this Review, the rational engineering of semiconductor-based photoanodes, including nanostructure design, elemental doping, defect engineering, and heterostructure construction, has been overviewed to introduce the recent advances for PEC cathodic protection. This Review aims to provide fundamental references and principles for the design and fabrication of highly efficient semiconductor photoanodes for PEC cathodic protection of metals.

基于半导体光阳极的光电化学（PEC）阴极保护技术将太阳能利用与金属防腐相结合，为开发环境友好型金属保护技术提供了一个前景广阔的平台。在这方面，半导体（如 TiO2、ZnO、SrTiO3、BiVO4 和 g-C3N4）具有合适的能带结构、良好的化学稳定性和低成本等优点，在候选光阳极中引起了广泛关注。然而，较差的光吸收特性和较高的光生电荷重组率严重限制了它们的光阴极保护性能。为了打破这些限制，人们对这些光阳极采用了不同的改性策略，以显著提高其光电阴极保护性能。本综述概述了基于半导体的光阳极的合理工程，包括纳米结构设计、元素掺杂、缺陷工程和异质结构构建，并介绍了 PEC 阴极保护的最新进展。本综述旨在为设计和制造用于 PEC 阴极保护金属的高效半导体光阳极提供基本参考和原理。

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引用次数: 0

Effects of molecular assembly on heterogeneous interactions in electronic and photovoltaic devices 分子组装对电子和光伏设备中异质相互作用的影响

Q2 CHEMISTRY, PHYSICAL

Chemical physics reviews

Pub Date : 2024-01-09 DOI: 10.1063/5.0173972

Manik Chandra Sil, Sonali Yadav, Ting-An Chen, Chandrasekaran Pitchai, Chih-Ming Chen

Heterogeneous junctions extensively exist in electronic and photovoltaic devices. Due to essential differences, the contacts of heterogeneous junctions are imperfect with structural discontinuity and chemical inconsistency, which have negative impacts on the mechanical, electrical, and thermal properties of devices. To improve the heterogeneous interactions, surface/interfacial modification approaches are developed in which molecular assembly engineering appears to be a promising strategy. Versatile functionalities can be accomplished by smart arrangement and design of the functional groups and geometry of the organic molecular layers. Specific functionality can also be maximized by well organization of the grafting orientation of molecules at the heterogeneous contacts. This article comprehensively reviews the approaches of molecular assembly engineering employed in the construction of the heterogeneous junctions to improve their mechanical, electrical, and thermal properties. Following the introduction of molecular assembly engineering at the target surface/interface, examples are introduced to show the efficacy of molecular assembly engineering on the interfacial adhesion, atomic interdiffusion, dielectric nature, charge injection and recombination, and thermoelectric property in electronic and photovoltaic devices.

异质结广泛存在于电子和光伏设备中。由于本质上的差异，异质结的接触并不完美，存在结构不连续性和化学不一致性，这对设备的机械、电气和热性能产生了负面影响。为了改善异质相互作用，人们开发了表面/界面修饰方法，其中分子组装工程似乎是一种很有前途的策略。通过巧妙地排列和设计官能团以及有机分子层的几何形状，可以实现多种功能。在异质接触处精心组织分子的接枝取向，也能最大限度地实现特定功能。本文全面回顾了在构建异质结时采用的分子组装工程方法，以改善其机械、电气和热性能。在介绍了目标表面/界面的分子组装工程后，文章举例说明了分子组装工程对电子和光伏设备中的界面粘附、原子间扩散、介电性质、电荷注入和重组以及热电性能的影响。

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引用次数: 0

Raman scattering monitoring of thin film materials for atomic layer etching/deposition in the nano-semiconductor process integration 纳米半导体工艺集成中原子层蚀刻/沉积薄膜材料的拉曼散射监测

Q2 CHEMISTRY, PHYSICAL

Chemical physics reviews

Pub Date : 2023-12-01 DOI: 10.1063/5.0147685

Jae Bin Kim, Dae Sik Kim, Jin Seok Kim, Jin Hyun Choe, Da Won Ahn, Eun Su Jung, Sung Gyu Pyo

According to Moore's law, the semiconductor industry is experiencing certain challenges in terms of adapting to highly sophisticated integrated technology. Therefore, controlling materials at the atomic scale is considered a mandatory requirement for further development. To this end, atomic layer deposition and etching skills are being increasingly researched as potential solutions. However, several considerations exist for adopting atomic technology with respect to surface analysis. This review primarily focuses on the use of Raman scattering for evaluating atomic-layered materials. Raman scattering analysis is expected to gradually expand as a semiconductor process and mass-production monitoring technology. As this can enhance the applications of this method, our review can form the basis for establishing Raman scattering analysis as a new trend for atomic-scale monitoring.

根据摩尔定律，半导体行业在适应高精尖集成技术方面正面临着一定的挑战。因此，在原子尺度上控制材料被认为是进一步发展的必然要求。为此，原子层沉积和蚀刻技术作为潜在的解决方案正得到越来越多的研究。不过，在表面分析方面采用原子技术还需要考虑几个因素。本综述主要侧重于使用拉曼散射评估原子层材料。拉曼散射分析作为一种半导体工艺和大规模生产监控技术，预计将逐步扩大。因此，我们的综述可为将拉曼散射分析确立为原子尺度监测的新趋势奠定基础。

引用次数: 0

Recent advances in open-shell mixed conductors—From molecular radicals to polymers 开壳混合导体的最新进展--从分子自由基到聚合物

Q2 CHEMISTRY, PHYSICAL

Chemical physics reviews

Pub Date : 2023-12-01 DOI: 10.1063/5.0163747

J. Ko, Quynh H. Nguyen, Quyen Vu Thi, Y. Joo

Mixed conductors have recently garnered attention in the chemical physicist community due to their distinctive conducting nature and numerous potential applications. These species transport charges via both ionic and electronic pathways, where the coupling between these pathways facilitates an alternative mode of charge transport. Among the various mixed conductors examined, stable open-shell organic compounds are emerging as a promising class of materials. They have the potential to supplant existing organic mixed conductors thanks to their superior conductivity, ease of processing, environmental stability, and functional adaptability. Notably, recent advancements in open-shell macromolecules have been remarkable, ranging from their unprecedented solid-state electrical conductivity to their versatile roles in electrochemistry. Similarly, recent strides in small molecular open-shell species deserve attention. The solid-state electronic properties of these small molecular radicals can be compared to those of macromolecular (non-)conjugated organics materials, and they also play a significant role in wet (electrolyte-based) chemistry. In this review article, we offer a comprehensive overview of open-shell organic compounds, encompassing both small and macromolecular radicals. We particularly emphasize their role as a mixed conductor in various applications, the unique context of each species, and the interconnections between them.

混合导体因其独特的导电性能和众多潜在应用，最近引起了化学物理学家的关注。这些物质通过离子和电子途径传输电荷，这些途径之间的耦合促进了电荷传输的另一种模式。在已研究过的各种混合导体中，稳定的开壳有机化合物正在成为一类前景广阔的材料。它们具有卓越的导电性、易加工性、环境稳定性和功能适应性，有望取代现有的有机混合导体。值得注意的是，开壳大分子最近取得了令人瞩目的进展，从其前所未有的固态导电性到其在电化学中的多功能作用，不一而足。同样，小分子开壳物种的最新进展也值得关注。这些小分子自由基的固态电子特性可与大分子（非）共轭有机材料相媲美，它们在湿化学（基于电解质的）中也发挥着重要作用。在这篇综述文章中，我们全面概述了开壳有机化合物，包括小分子和大分子自由基。我们特别强调了它们在各种应用中作为混合导体的作用、每个物种的独特背景以及它们之间的相互联系。

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引用次数: 0

Electron and ion behaviors at the graphene/metal interface during the acidic water electrolysis 酸性水电解过程中石墨烯/金属界面上的电子和离子行为

Q2 CHEMISTRY, PHYSICAL

Chemical physics reviews

Pub Date : 2023-12-01 DOI: 10.1063/5.0175537

Yue Xu, Yingjian He, Shaofeng Wang, Zhaomeng Wu, Haolin Hu, Samuel Jeong, Xi Lin, Kailong Hu

Hydrogen produced via proton exchange membrane (PEM) water electrolysis has been considered as one of the most promising alternatives to store and convert energy derived from renewable sources. The acidic environment within the PEM electrolyzer poses challenges to the metal-based electrocatalysts employed in both cathode and anode, necessitating a high level of corrosion resistance. This review provides a comprehensive overview of the emerging graphene-encapsulated metals in catalyzing cathodic and anodic reactions of water electrolysis under acidic media. The two major behaviors occurring at the graphene/metal interface, i.e., the electron transfer and ionic penetration, are systematically discussed owing to the experimental results and computational simulations. The correlation between the graphene shell and underlying metal, as well as their impact on the electron and ion behaviors, is further revealed. The mechanisms governed by the electron and ion behaviors are proposed for graphene encapsulated metal catalysts, providing valuable insights toward the design of cutting-edge metal catalysts for the acidic water electrolysis.

通过质子交换膜（PEM）水电解产生的氢被认为是储存和转换可再生能源的最有前途的替代方法之一。PEM 电解槽中的酸性环境对阴极和阳极中使用的金属基电催化剂提出了挑战，要求其具有很高的耐腐蚀性。本综述全面概述了在酸性介质下催化水电解阴极和阳极反应的新兴石墨烯封装金属。通过实验结果和计算模拟，系统地讨论了石墨烯/金属界面上发生的两种主要行为，即电子转移和离子渗透。进一步揭示了石墨烯外壳和底层金属之间的相关性，以及它们对电子和离子行为的影响。提出了石墨烯封装金属催化剂的电子和离子行为机理，为设计用于酸性水电解的尖端金属催化剂提供了宝贵的见解。

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引用次数: 0

Nanoscale and ultrafast in situ techniques to probe plasmon photocatalysis 探测等离子体光催化的纳米级和超快原位技术

Q2 CHEMISTRY, PHYSICAL

Chemical physics reviews

Pub Date : 2023-12-01 DOI: 10.1063/5.0163354

Claire C. Carlin, Alan X. Dai, Alexander Al-Zubeidi, Emma M. Simmerman, Hyuncheol Oh, Niklas Gross, Stephen A. Lee, Stephan Link, C. Landes, Felipe H. da Jornada, Jennifer A. Dionne

Plasmonic photocatalysis uses the light-induced resonant oscillation of free electrons in a metal nanoparticle to concentrate optical energy for driving chemical reactions. By altering the joint electronic structure of the catalyst and reactants, plasmonic catalysis enables reaction pathways with improved selectivity, activity, and catalyst stability. However, designing an optimal catalyst still requires a fundamental understanding of the underlying plasmonic mechanisms at the spatial scales of single particles, at the temporal scales of electron transfer, and in conditions analogous to those under which real reactions will operate. Thus, in this review, we provide an overview of several of the available and developing nanoscale and ultrafast experimental approaches, emphasizing those that can be performed in situ. Specifically, we discuss high spatial resolution optical, tip-based, and electron microscopy techniques; high temporal resolution optical and x-ray techniques; and emerging ultrafast optical, x-ray, tip-based, and electron microscopy techniques that simultaneously achieve high spatial and temporal resolution. Ab initio and classical continuum theoretical models play an essential role in guiding and interpreting experimental exploration, and thus, these are also reviewed and several notable theoretical insights are discussed.

等离子体光催化利用金属纳米颗粒中自由电子的光诱导共振振荡来集中光能来驱动化学反应。通过改变催化剂和反应物的连接电子结构，等离子体催化使反应途径具有更高的选择性、活性和催化剂稳定性。然而，设计一种最佳的催化剂仍然需要对潜在的等离子体机制有一个基本的了解，在单粒子的空间尺度上，在电子转移的时间尺度上，在类似于真实反应发生的条件下。因此，在本综述中，我们概述了几种可用的和正在开发的纳米尺度和超快实验方法，重点介绍了那些可以在原位进行的方法。具体来说，我们讨论了高空间分辨率光学，尖端和电子显微镜技术;高时间分辨率光学和x射线技术;以及新兴的超快光学、x射线、尖端和电子显微镜技术，这些技术同时实现了高空间和时间分辨率。从头算和经典连续体理论模型在指导和解释实验探索方面发挥着重要作用，因此，本文也对它们进行了回顾，并讨论了一些值得注意的理论见解。

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引用次数: 0

Embrace the darkness: An experimental perspective on organic exciton–polaritons 拥抱黑暗:有机激子极化的实验视角

Q2 CHEMISTRY, PHYSICAL

Chemical physics reviews

Pub Date : 2023-11-13 DOI: 10.1063/5.0168948

Thomas Khazanov, Suman Gunasekaran, Aleesha George, Rana Lomlu, Soham Mukherjee, Andrew J. Musser

Organic polaritonics has emerged as a captivating interdisciplinary field that marries the complexities of organic photophysics with the fundamental principles of quantum optics. By harnessing strong light–matter coupling in organic materials, exciton–polaritons offer unique opportunities for advanced device performance, including enhanced energy transport and low-threshold lasing, as well as new functionalities like polariton chemistry. In this review, we delve into the foundational principles of exciton–polaritons from an experimental perspective, highlighting the key states, processes, and timescales that govern polariton phenomena. Our review centers on the spectroscopy of exciton–polaritons. We overview the primary spectroscopic approaches that reveal polariton phenomena, and we discuss the challenges in disentangling polaritonic signatures from spectral artifacts. We discuss how organic materials, due to their complex photophysics and disordered nature, not only present challenges to the conventional polariton models but also provide opportunities for new physics, like manipulating dark electronic states. As the research field continues to grow, with increasingly complex materials and devices, this review serves as a valuable introductory guide for researchers navigating the intricate landscape of organic polaritonics.

有机极化电子学已经成为一个迷人的跨学科领域，它将有机光物理学的复杂性与量子光学的基本原理结合在一起。通过利用有机材料中的强光-物质耦合，激子-极化子为先进的设备性能提供了独特的机会，包括增强的能量传输和低阈值激光，以及极化子化学等新功能。在这篇综述中，我们从实验的角度深入研究了激子-极化子的基本原理，强调了控制极化子现象的关键状态、过程和时间尺度。我们的综述集中在激子-极化子的光谱学上。我们概述了揭示极化现象的主要光谱方法，并讨论了从光谱伪影中分离极化特征的挑战。我们讨论了有机材料，由于其复杂的光物理和无序的性质，不仅对传统的极化子模型提出了挑战，而且为新的物理，如操纵暗电子态，提供了机会。随着研究领域的不断发展，材料和器件越来越复杂，本综述为研究人员导航有机极化电子学的复杂景观提供了有价值的入门指南。

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引用次数: 0

Higher manganese silicides: A Nowotny chimney ladder phase for thermoelectric applications 高锰硅化物:热电应用的诺沃特尼烟囱梯相

Q2 CHEMISTRY, PHYSICAL

Chemical physics reviews

Pub Date : 2023-10-23 DOI: 10.1063/5.0167220

Nagendra S. Chauhan, Yuzuru Miyazaki

Nowotny chimney ladder (NCL) phases are intermetallic binary compounds that typically crystallize in a tetragonal crystal structure and constitute of two separate subsystems. The rich solid-state chemistry of NCL phases inherits fascinating lattice dynamics with unique abilities for structural modifications. As an extensively studied energy material for the thermoelectric application, we overview the emerging aspects for structural interpretation in higher manganese silicides (MnSiγ), a prominently explored example of NCL phase. The progress in understanding the incommensurate composite crystals of MnSiγ is discussed to highlight its functional crystallography for proposing the effective strategies to attain favorable modification of transport properties of charge carriers (concentration, mobility, effective mass), and phonons (lattice thermal conductivity). The application potential and prospective strategies for enabling the rational optimization of the dimensionless thermoelectric figure of merit (zT) are examined, and the possibilities of chemical modification in MnSiγ and related NCL phases are presented.

诺沃特尼烟囱梯相(NCL)是金属间二元化合物，通常以四方晶体结构结晶，由两个独立的子系统组成。NCL相丰富的固态化学继承了迷人的晶格动力学和独特的结构修饰能力。作为热电应用中广泛研究的能源材料，我们概述了高锰硅化物(MnSiγ)结构解释的新兴方面，这是NCL相的一个突出探索的例子。本文讨论了对MnSiγ不匹配复合晶体的研究进展，重点介绍了其功能晶体学，并提出了有效的策略，以获得对载流子(浓度、迁移率、有效质量)和声子(晶格热导率)的有利修饰。研究了合理优化无因次热电性能图(zT)的应用潜力和前瞻性策略，并提出了在MnSiγ和相关NCL相中进行化学改性的可能性。

引用次数: 0

Host–guest interactions in framework materials: Insight from modeling 框架材料中的主客交互:来自建模的洞察

Q2 CHEMISTRY, PHYSICAL

Chemical physics reviews

Pub Date : 2023-10-20 DOI: 10.1063/5.0144827

Michelle Ernst, Jack D. Evans, Ganna Gryn'ova

The performance of metal–organic and covalent organic framework materials in sought-after applications—capture, storage, and delivery of gases and molecules, and separation of their mixtures—heavily depends on the host–guest interactions established inside the pores of these materials. Computational modeling provides information about the structures of these host–guest complexes and the strength and nature of the interactions present at a level of detail and precision that is often unobtainable from experiment. In this Review, we summarize the key simulation techniques spanning from molecular dynamics and Monte Carlo methods to correlate ab initio approaches and energy, density, and wavefunction partitioning schemes. We provide illustrative literature examples of their uses in analyzing and designing organic framework hosts. We also describe modern approaches to the high-throughput screening of thousands of existing and hypothetical metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) and emerging machine learning techniques for predicting their properties and performances. Finally, we discuss the key methodological challenges on the path toward computation-driven design and reliable prediction of high-performing MOF and COF adsorbents and catalysts and suggest possible solutions and future directions in this exciting field of computational materials science.

金属有机和共价有机框架材料的性能在广受欢迎的应用中——气体和分子的捕获、储存和输送，以及它们混合物的分离——在很大程度上取决于这些材料孔隙内建立的主客体相互作用。计算模型提供了关于这些主客体复合物结构的信息，以及在通常无法从实验中获得的细节和精度水平上存在的相互作用的强度和性质。在这篇综述中，我们总结了从分子动力学和蒙特卡罗方法到从头算方法和能量、密度和波函数划分方案的关键模拟技术。我们提供了它们在分析和设计有机框架主机中的应用的说明性文献示例。我们还描述了对数千种现有和假设的金属有机框架(mof)和共价有机框架(COFs)进行高通量筛选的现代方法，以及用于预测其性质和性能的新兴机器学习技术。最后，我们讨论了在实现高性能MOF和COF吸附剂和催化剂的计算驱动设计和可靠预测的道路上的关键方法挑战，并提出了在这个令人兴奋的计算材料科学领域可能的解决方案和未来的方向。

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引用次数: 0