Raphael M Jay, Kristjan Kunnus, Philippe Wernet, Kelly J Gaffney
{"title":"用超快软x射线光谱捕捉过渡金属配合物的原子特异性电子结构动力学。","authors":"Raphael M Jay, Kristjan Kunnus, Philippe Wernet, Kelly J Gaffney","doi":"10.1146/annurev-physchem-082820-020236","DOIUrl":null,"url":null,"abstract":"<p><p>The atomic specificity of X-ray spectroscopies provides a distinct perspective on molecular electronic structure. For 3<i>d</i> metal coordination and organometallic complexes, the combination of metal- and ligand-specific X-ray spectroscopies directly interrogates metal-ligand covalency-the hybridization of metal and ligand electronic states. Resonant inelastic X-ray scattering (RIXS), the X-ray analog of resonance Raman scattering, provides access to all classes of valence excited states in transition-metal complexes, making it a particularly powerful means of characterizing the valence electronic structure of 3<i>d</i> metal complexes. Recent advances in X-ray free-electron laser sources have enabled RIXS to be extended to the ultrafast time domain. We review RIXS studies of two archetypical photochemical processes: charge-transfer excitation in ferricyanide and ligand photodissociation in iron pentacarbonyl. These studies demonstratefemtosecond-resolution RIXS can directly characterize the time-evolving electronic structure, including the evolution of the metal-ligand covalency.</p>","PeriodicalId":7967,"journal":{"name":"Annual review of physical chemistry","volume":null,"pages":null},"PeriodicalIF":11.7000,"publicationDate":"2022-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"4","resultStr":"{\"title\":\"Capturing Atom-Specific Electronic Structural Dynamics of Transition-Metal Complexes with Ultrafast Soft X-Ray Spectroscopy.\",\"authors\":\"Raphael M Jay, Kristjan Kunnus, Philippe Wernet, Kelly J Gaffney\",\"doi\":\"10.1146/annurev-physchem-082820-020236\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The atomic specificity of X-ray spectroscopies provides a distinct perspective on molecular electronic structure. For 3<i>d</i> metal coordination and organometallic complexes, the combination of metal- and ligand-specific X-ray spectroscopies directly interrogates metal-ligand covalency-the hybridization of metal and ligand electronic states. Resonant inelastic X-ray scattering (RIXS), the X-ray analog of resonance Raman scattering, provides access to all classes of valence excited states in transition-metal complexes, making it a particularly powerful means of characterizing the valence electronic structure of 3<i>d</i> metal complexes. Recent advances in X-ray free-electron laser sources have enabled RIXS to be extended to the ultrafast time domain. We review RIXS studies of two archetypical photochemical processes: charge-transfer excitation in ferricyanide and ligand photodissociation in iron pentacarbonyl. These studies demonstratefemtosecond-resolution RIXS can directly characterize the time-evolving electronic structure, including the evolution of the metal-ligand covalency.</p>\",\"PeriodicalId\":7967,\"journal\":{\"name\":\"Annual review of physical chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":11.7000,\"publicationDate\":\"2022-04-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"4\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Annual review of physical chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1146/annurev-physchem-082820-020236\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2022/1/5 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Annual review of physical chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1146/annurev-physchem-082820-020236","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2022/1/5 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Capturing Atom-Specific Electronic Structural Dynamics of Transition-Metal Complexes with Ultrafast Soft X-Ray Spectroscopy.
The atomic specificity of X-ray spectroscopies provides a distinct perspective on molecular electronic structure. For 3d metal coordination and organometallic complexes, the combination of metal- and ligand-specific X-ray spectroscopies directly interrogates metal-ligand covalency-the hybridization of metal and ligand electronic states. Resonant inelastic X-ray scattering (RIXS), the X-ray analog of resonance Raman scattering, provides access to all classes of valence excited states in transition-metal complexes, making it a particularly powerful means of characterizing the valence electronic structure of 3d metal complexes. Recent advances in X-ray free-electron laser sources have enabled RIXS to be extended to the ultrafast time domain. We review RIXS studies of two archetypical photochemical processes: charge-transfer excitation in ferricyanide and ligand photodissociation in iron pentacarbonyl. These studies demonstratefemtosecond-resolution RIXS can directly characterize the time-evolving electronic structure, including the evolution of the metal-ligand covalency.
期刊介绍:
The Annual Review of Physical Chemistry has been published since 1950 and is a comprehensive resource for significant advancements in the field. It encompasses various sub-disciplines such as biophysical chemistry, chemical kinetics, colloids, electrochemistry, geochemistry and cosmochemistry, chemistry of the atmosphere and climate, laser chemistry and ultrafast processes, the liquid state, magnetic resonance, physical organic chemistry, polymers and macromolecules, and others.