Chemical physics reviews最新文献_第7页

Charge transport in doped conjugated polymers for organic thermoelectrics 有机热电用掺杂共轭聚合物中的电荷输运

Chemical physics reviews Pub Date : 2022-06-01 DOI: 10.1063/5.0080820

Dorothea Scheunemann, Emmy Järsvall, Jian Liu, D. Beretta, S. Fabiano, M. Caironi, M. Kemerink, Christian Müller

{"title":"Charge transport in doped conjugated polymers for organic thermoelectrics","authors":"Dorothea Scheunemann, Emmy Järsvall, Jian Liu, D. Beretta, S. Fabiano, M. Caironi, M. Kemerink, Christian Müller","doi":"10.1063/5.0080820","DOIUrl":"https://doi.org/10.1063/5.0080820","url":null,"abstract":"Research on conjugated polymers for thermoelectric applications has made tremendous progress in recent years, which is accompanied by surging interest in molecular doping as a means to achieve the high electrical conductivities that are required. A detailed understanding of the complex relationship between the doping process, the structural as well as energetic properties of the polymer films, and the resulting thermoelectric behavior is slowly emerging. This review summarizes recent developments and strategies that permit enhancing the electrical conductivity of p- and n-type conjugated polymers via molecular doping. The impact of the chemical design of both the polymer and the dopant, the processing conditions, and the resulting nanostructure on the doping efficiency and stability of the doped state are discussed. Attention is paid to the interdependence of the electrical and thermal transport characteristics of semiconductor host-dopant systems and the Seebeck coefficient. Strategies that permit to improve the thermoelectric performance, such as an uniaxial alignment of the polymer backbone in both bulk and thin film geometries, manipulation of the dielectric constant of the polymer, and the variation of the dopant size, are explored. A combination of theory and experiment is predicted to yield new chemical design principles and processing schemes that will ultimately give rise to the next generation of organic thermoelectric materials.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47507645","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 11

Emergence of ligand-to-metal charge transfer in homogeneous photocatalysis and photosensitization 均相光催化和光敏化中配体到金属电荷转移的出现

Chemical physics reviews Pub Date : 2022-06-01 DOI: 10.1063/5.0086718

Chenfei Li, X. Kong, Z. Tan, C. Yang, Han Sen Soo

{"title":"Emergence of ligand-to-metal charge transfer in homogeneous photocatalysis and photosensitization","authors":"Chenfei Li, X. Kong, Z. Tan, C. Yang, Han Sen Soo","doi":"10.1063/5.0086718","DOIUrl":"https://doi.org/10.1063/5.0086718","url":null,"abstract":"Light energy can be harnessed by photosensitizers or photocatalysts so that some chemical reactions can be carried out under milder conditions compared to the traditional heat-driven processes. To facilitate the photo-driven reactions, a large variety of chromophores that are operated via charge transfer excitations have been reported because of their typically longer excited-state lifetimes, which are the key to the downstream photochemical processes. Although both metal-to-ligand charge transfers and ligand-to-metal charge transfers are well-established light absorption pathways; the former has been widely adopted in photocatalysis, whereas the latter has recently taken on greater importance in photosensitization applications. In this article, we review the latest developments on ligand-to-metal charge transfer photosensitization by molecular complexes across the periodic table by focusing homogeneous photocatalysis and the use of photophysical measurements and computational calculations to understand the electronic structures, photochemical processes, structure–activity relationships, and reaction mechanisms. We also present our perspectives on the possible future developments in the field.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47561478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 6

Strategies for accessing photosensitizers with extreme redox potentials 获取具有极端氧化还原电位的光敏剂的策略

Chemical physics reviews Pub Date : 2022-06-01 DOI: 10.1063/5.0084554

Dooyoung Kim, Thomas S. Teets

{"title":"Strategies for accessing photosensitizers with extreme redox potentials","authors":"Dooyoung Kim, Thomas S. Teets","doi":"10.1063/5.0084554","DOIUrl":"https://doi.org/10.1063/5.0084554","url":null,"abstract":"Photoredox catalysis has been prominent in many applications, including solar fuels, organic synthesis, and polymer chemistry. Photocatalytic activity directly depends on the photophysical and electrochemical properties of photocatalysts in both the ground state and excited state. Controlling those properties, therefore, is imperative to achieve the desired photocatalytic activity. Redox potential is one important factor that impacts both the thermodynamic and kinetic aspects of key elementary steps in photoredox catalysis. In many challenging reactions in organic synthesis, high redox potentials of the substrates hamper the reaction, leading to slow conversion. Thus, the development of photocatalysts with extreme redox potentials, accompanied by potent reducing or oxidizing power, is required to execute high-yielding thermodynamically demanding reactions. In this review, we will introduce strategies for accessing extreme redox potentials in photocatalytic transformations. These include molecular design strategies for preparing photosensitizers that are exceptionally strong ground-state or excited-state reductants or oxidants, highlighting both organic and metal-based photosensitizers. We also outline methodological approaches for accessing extreme redox potentials, using two-photon activation, or combined electrochemical/photochemical strategies to generate potent redox reagents from precursors that have milder potentials.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45886176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 10

Ultrafast photo-induced processes in complex environments: The role of accuracy in excited-state energy potentials and initial conditions 复杂环境下的超快光诱导过程:精度在激发态能势和初始条件中的作用

Chemical physics reviews Pub Date : 2022-06-01 DOI: 10.1063/5.0085512

A. Petrone, F. Perrella, Federico Coppola, Luigi Crisci, Greta Donati, P. Cimino, N. Rega

{"title":"Ultrafast photo-induced processes in complex environments: The role of accuracy in excited-state energy potentials and initial conditions","authors":"A. Petrone, F. Perrella, Federico Coppola, Luigi Crisci, Greta Donati, P. Cimino, N. Rega","doi":"10.1063/5.0085512","DOIUrl":"https://doi.org/10.1063/5.0085512","url":null,"abstract":"Light induces non-equilibrium time evolving molecular phenomena. The computational modeling of photo-induced processes in large systems, embedded in complex environments (i.e., solutions, proteins, materials), demands for a quantum and statistical mechanic treatment to achieve the required accuracy in the description of both the excited-state energy potentials and the choice of the initial conditions for dynamical simulations. On the other hand, the theoretical investigation on the atomistic scale of times and sizes of the ultrafast photo-induced reactivity and non-equilibrium relaxation dynamics right upon excitation requests tailored computational protocols. These methods often exploit hierarchic computation schemes, where a large part of the degrees of freedom are required to be treated explicitly to achieve the right accuracy. Additionally, part of the explicit system needs to be treated at ab initio level, where density functional theory, using hybrid functionals, represents a good compromise between accuracy and computational cost, when proton transfers, non-covalent interactions, and hydrogen bond dynamics play important roles. Thus, the modeling strategies presented in this review stress the importance of hierarchical quantum/molecular mechanics with effective non-periodic boundary conditions and efficient phase-sampling schemes to achieve chemical accuracy in ultrafast time-resolved spectroscopy and photo-induced phenomena. These approaches can allow explicit and accurate treatment of molecule/environment interactions, including also the electrostatic and dispersion forces of the bulk. At the same time, the specificities of the different case studies of photo-induced phenomena in solutions and biological environments are highlighted and discussed, with special attention to the computational and modeling challenges.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"58563775","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 4

Methane storage in flexible and dynamical metal–organic frameworks 柔性和动态金属-有机框架中的甲烷储存

Chemical physics reviews Pub Date : 2022-06-01 DOI: 10.1063/5.0072805

K. Forrest, G. Verma, Yingxiang Ye, Junyu Ren, Shengqian Ma, Tony Pham, Brian Space

引用次数: 4

Molecular qubits based on photogenerated spin-correlated radical pairs for quantum sensing 基于光生自旋相关自由基对的量子传感分子量子比特

Chemical physics reviews Pub Date : 2022-06-01 DOI: 10.1063/5.0084072

Tomoyasu Mani

{"title":"Molecular qubits based on photogenerated spin-correlated radical pairs for quantum sensing","authors":"Tomoyasu Mani","doi":"10.1063/5.0084072","DOIUrl":"https://doi.org/10.1063/5.0084072","url":null,"abstract":"Photogenerated spin-correlated radical pairs (SCRPs) in electron donor–bridge–acceptor (D–B–A) molecules can act as molecular qubits and inherently spin qubit pairs. SCRPs can take singlet and triplet spin states, comprising the quantum superposition state. Their synthetic accessibility and well-defined structures, together with their ability to be prepared in an initially pure, entangled spin state and optical addressability, make them one of the promising avenues for advancing quantum information science. Coherence between two spin states and spin selective electron transfer reactions form the foundation of using SCRPs as qubits for sensing. We can exploit the unique sensitivity of the spin dynamics of SCRPs to external magnetic fields for sensing applications including resolution-enhanced imaging, magnetometers, and magnetic switch. Molecular quantum sensors, if realized, can provide new technological developments beyond what is possible with classical counterparts. While the community of spin chemistry has actively investigated magnetic field effects on chemical reactions via SCRPs for several decades, we have not yet fully exploited the synthetic tunability of molecular systems to our advantage. This review offers an introduction to the photogenerated SCRPs-based molecular qubits for quantum sensing, aiming to lay the foundation for researchers new to the field and provide a basic reference for researchers active in the field. We focus on the basic principles necessary to construct molecular qubits based on SCRPs and the examples in quantum sensing explored to date from the perspective of the experimentalist.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42131592","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 13

Recent progress in the theory of bulk photovoltaic effect 体光伏效应理论的最新进展

Chemical physics reviews Pub Date : 2022-06-01 DOI: 10.1063/5.0101513

Zhenbang Dai, A. Rappe

{"title":"Recent progress in the theory of bulk photovoltaic effect","authors":"Zhenbang Dai, A. Rappe","doi":"10.1063/5.0101513","DOIUrl":"https://doi.org/10.1063/5.0101513","url":null,"abstract":"The bulk photovoltaic effect (BPVE) occurs in solids with broken inversion symmetry and refers to DC generation due to uniform illumination, without the need of heterostructures or interfaces, a feature that is distinct from the traditional photovoltaic effect. Its existence has been demonstrated almost 50 years ago, but predictive theories only appeared in the last ten years, allowing for the identification of different mechanisms and the determination of their relative importance in real materials. It is now generally accepted that there is an intrinsic mechanism that is insensitive to scattering, called shift current, where first-principles calculations can now give highly accurate predictions. Another important but more extrinsic mechanism, called ballistic current, is also attracting a great deal of attention, but due to the complicated scattering processes, its numerical calculation for real materials is only made possible quite recently. In addition, an intrinsic ballistic current, usually referred to as injection current, will appear under circularly polarized light and has wide application in experiments. In this review, experiments that are pertinent to the theory development are reviewed, and a significant portion is devoted to discussing the recent progress in the theories of BPVE and their numerical implementations. As a demonstration of the capability of the newly developed theories, a brief review of the materials' design strategies enabled by the theory development is given. Finally, remaining questions in the BPVE field and possible future directions are discussed to inspire further investigations.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45550893","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 12

Emerging opportunities with metal-organic framework electrosynthetic platforms 金属有机框架电合成平台的新兴机遇

Chemical physics reviews Pub Date : 2022-06-01 DOI: 10.1063/5.0090147

Kiran Kuruvinashetti, Junnan Li, Yuxuan Zhang, Hossein Bemana, Morgan McKee, N. Kornienko

{"title":"Emerging opportunities with metal-organic framework electrosynthetic platforms","authors":"Kiran Kuruvinashetti, Junnan Li, Yuxuan Zhang, Hossein Bemana, Morgan McKee, N. Kornienko","doi":"10.1063/5.0090147","DOIUrl":"https://doi.org/10.1063/5.0090147","url":null,"abstract":"The development of electrochemical technologies is becoming increasingly important due to their growing part in renewable energy conversion and storage. Within this context, metal organic frameworks (MOFs) are finding an important role as electrocatalysts. Specifically, their molecularly defined structure across several lengths scales endows them functionality not accessible with conventional heterogeneous catalysts. To this end, this perspective will focus on the unique features within MOFs and their analogs that enable them to carry out electrocatalytic reactions in unique ways to synthesize fuels and value-added chemicals from abundant building blocks like CO2 and N2. We start with a brief overview of the initial advent of MOF electrocatalysts prior to moving to overview the forefront of the field of MOF-based electrosynthesis. The main discussion focuses on three principal directions in MOF-based electrosynthesis: multifunctional active sites, electronic modulation, and catalytic microenvironments. To conclude, we identify several challenges in the next stage of MOF electrocatalyst development and offer several key directions to take as the field matures.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43282765","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 1

The exact exchange–correlation potential in time-dependent density functional theory: Choreographing electrons with steps and peaks 含时密度泛函理论中的精确交换-相关势：用台阶和峰值编排电子

Chemical physics reviews Pub Date : 2022-05-07 DOI: 10.1063/5.0096627

D. Dar, L. Lacombe, N. Maitra

引用次数: 2

Theoretical design of two-dimensional visible light-driven photocatalysts for overall water splitting 二维可见光驱动全水分解光催化剂的理论设计

Chemical physics reviews Pub Date : 2022-03-01 DOI: 10.1063/5.0079803

Cen-Feng Fu, Xiaojun Wu, Jinlong Yang

{"title":"Theoretical design of two-dimensional visible light-driven photocatalysts for overall water splitting","authors":"Cen-Feng Fu, Xiaojun Wu, Jinlong Yang","doi":"10.1063/5.0079803","DOIUrl":"https://doi.org/10.1063/5.0079803","url":null,"abstract":"Hydrogen production from water via photocatalytic water splitting has attracted great interest due to the increasing challenge from energy and environment. The light harvest, electron–hole separation, and catalytic activity are keys to enhance the efficiency of solar energy utilization, which stimulates the development of high-performance photocatalysts. In recent years, two-dimensional (2D) materials have attracted much attention due to their extremely large specific surface area, shortened carrier migration path, and excellent optical properties, but it is still a challenge to realize overall water splitting under visible light with 2D material photocatalysts experimentally. Density functional theory-based first-principles calculations provide a quicker and lower cost approach in material design than experimental exploration. In this review, recent advances in design of 2D material photocatalysts, including metal-containing, metal-free, and heterojunction materials, for photocatalytic water splitting are presented from a theoretical perspective. Future opportunities and challenges in theoretical design of 2D material photocatalysts toward overall water splitting are also included.","PeriodicalId":72559,"journal":{"name":"Chemical physics reviews","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48128401","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 7