{"title":"拉曼散射的双重性。","authors":"Wei Min*, and , Xin Gao, ","doi":"10.1021/acs.accounts.4c00159","DOIUrl":null,"url":null,"abstract":"<p >First predicted more than 100 years ago, Raman scattering is a cornerstone of photonics, spectroscopy, and imaging. The conventional framework of understanding Raman scattering was built on Raman cross section σ<sub>Raman</sub>. Carrying a dimension of area, σ<sub>Raman</sub> characterizes the interaction strength between light and molecules during inelastic scattering. The numerical values of σ<sub>Raman</sub> turn out to be many orders of magnitude smaller in comparison to the linear absorption cross sections σ<sub>Absorption</sub> of similar molecular systems. Such an enormous gap has been the reason for researchers to believe the extremely feeble Raman scattering ever since its discovery. However, this prevailing picture is conceptually problematic or at least incomplete due to the fact that Raman scattering and linear absorption belong to different orders of light–matter interaction.</p><p >In this Account, we will summarize an alternate way to think about Raman scattering, which we term stimulated response formulation. To capture the third-order interaction nature of Raman scattering, we introduced stimulated Raman cross section, σ<sub>SRS</sub>, defined as the <i>intrinsic</i> molecular property in response to the external photon fluxes. Foremost, experimental measurement of σ<sub>SRS</sub> turns out to be not weak at all or even larger when fairly compared with electronic counterparts of the same order. The analytical expression for σ<sub>SRS</sub> derived from quantum electrodynamics also supports the measurement and proves that σ<sub>SRS</sub> is intrinsically strong. Hence, σ<sub>Raman</sub> and σ<sub>SRS</sub> can be extremely small and large, respectively, for the same molecule at the same time. Our subsequent theoretical studies show that stimulated response formulation can unify spontaneous emission, stimulated emission, spontaneous Raman, and stimulated Raman via eq 10, in a coherent and symmetric way. In particular, an Einstein-coefficient-like equation, eq 12a, was derived, showing that σ<sub>Raman</sub> can be explicitly expressed as σ<sub>SRS</sub> multiplied by an effective photon flux arising from zero-point fluctuation of the vacuum. The feeble vacuum fluctuation hence explains how σ<sub>SRS</sub> can be intrinsically strong while, at the same time, σ<sub>Raman</sub> ends up being many orders of magnitude smaller when both compared to the electronic counterparts. These two sides of the same coin prompted us to propose “the duality of Raman scattering” (Table 1). Finally, this formulation naturally leads to a quantitative treatment of stimulated Raman scattering (SRS) microscopy, providing an intuitive, molecule-centric explanation as to how SRS microscopy can outperform regular Raman microscopy. Hence, as unveiled by the new formulation, a duality of Raman scattering has emerged, with implications for both fundamental science and practical technology.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4000,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"The Duality of Raman Scattering\",\"authors\":\"Wei Min*, and , Xin Gao, \",\"doi\":\"10.1021/acs.accounts.4c00159\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >First predicted more than 100 years ago, Raman scattering is a cornerstone of photonics, spectroscopy, and imaging. The conventional framework of understanding Raman scattering was built on Raman cross section σ<sub>Raman</sub>. Carrying a dimension of area, σ<sub>Raman</sub> characterizes the interaction strength between light and molecules during inelastic scattering. The numerical values of σ<sub>Raman</sub> turn out to be many orders of magnitude smaller in comparison to the linear absorption cross sections σ<sub>Absorption</sub> of similar molecular systems. Such an enormous gap has been the reason for researchers to believe the extremely feeble Raman scattering ever since its discovery. However, this prevailing picture is conceptually problematic or at least incomplete due to the fact that Raman scattering and linear absorption belong to different orders of light–matter interaction.</p><p >In this Account, we will summarize an alternate way to think about Raman scattering, which we term stimulated response formulation. To capture the third-order interaction nature of Raman scattering, we introduced stimulated Raman cross section, σ<sub>SRS</sub>, defined as the <i>intrinsic</i> molecular property in response to the external photon fluxes. Foremost, experimental measurement of σ<sub>SRS</sub> turns out to be not weak at all or even larger when fairly compared with electronic counterparts of the same order. The analytical expression for σ<sub>SRS</sub> derived from quantum electrodynamics also supports the measurement and proves that σ<sub>SRS</sub> is intrinsically strong. Hence, σ<sub>Raman</sub> and σ<sub>SRS</sub> can be extremely small and large, respectively, for the same molecule at the same time. Our subsequent theoretical studies show that stimulated response formulation can unify spontaneous emission, stimulated emission, spontaneous Raman, and stimulated Raman via eq 10, in a coherent and symmetric way. In particular, an Einstein-coefficient-like equation, eq 12a, was derived, showing that σ<sub>Raman</sub> can be explicitly expressed as σ<sub>SRS</sub> multiplied by an effective photon flux arising from zero-point fluctuation of the vacuum. The feeble vacuum fluctuation hence explains how σ<sub>SRS</sub> can be intrinsically strong while, at the same time, σ<sub>Raman</sub> ends up being many orders of magnitude smaller when both compared to the electronic counterparts. These two sides of the same coin prompted us to propose “the duality of Raman scattering” (Table 1). Finally, this formulation naturally leads to a quantitative treatment of stimulated Raman scattering (SRS) microscopy, providing an intuitive, molecule-centric explanation as to how SRS microscopy can outperform regular Raman microscopy. Hence, as unveiled by the new formulation, a duality of Raman scattering has emerged, with implications for both fundamental science and practical technology.</p>\",\"PeriodicalId\":1,\"journal\":{\"name\":\"Accounts of Chemical Research\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":16.4000,\"publicationDate\":\"2024-06-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Accounts of Chemical Research\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.accounts.4c00159\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Accounts of Chemical Research","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.accounts.4c00159","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
First predicted more than 100 years ago, Raman scattering is a cornerstone of photonics, spectroscopy, and imaging. The conventional framework of understanding Raman scattering was built on Raman cross section σRaman. Carrying a dimension of area, σRaman characterizes the interaction strength between light and molecules during inelastic scattering. The numerical values of σRaman turn out to be many orders of magnitude smaller in comparison to the linear absorption cross sections σAbsorption of similar molecular systems. Such an enormous gap has been the reason for researchers to believe the extremely feeble Raman scattering ever since its discovery. However, this prevailing picture is conceptually problematic or at least incomplete due to the fact that Raman scattering and linear absorption belong to different orders of light–matter interaction.
In this Account, we will summarize an alternate way to think about Raman scattering, which we term stimulated response formulation. To capture the third-order interaction nature of Raman scattering, we introduced stimulated Raman cross section, σSRS, defined as the intrinsic molecular property in response to the external photon fluxes. Foremost, experimental measurement of σSRS turns out to be not weak at all or even larger when fairly compared with electronic counterparts of the same order. The analytical expression for σSRS derived from quantum electrodynamics also supports the measurement and proves that σSRS is intrinsically strong. Hence, σRaman and σSRS can be extremely small and large, respectively, for the same molecule at the same time. Our subsequent theoretical studies show that stimulated response formulation can unify spontaneous emission, stimulated emission, spontaneous Raman, and stimulated Raman via eq 10, in a coherent and symmetric way. In particular, an Einstein-coefficient-like equation, eq 12a, was derived, showing that σRaman can be explicitly expressed as σSRS multiplied by an effective photon flux arising from zero-point fluctuation of the vacuum. The feeble vacuum fluctuation hence explains how σSRS can be intrinsically strong while, at the same time, σRaman ends up being many orders of magnitude smaller when both compared to the electronic counterparts. These two sides of the same coin prompted us to propose “the duality of Raman scattering” (Table 1). Finally, this formulation naturally leads to a quantitative treatment of stimulated Raman scattering (SRS) microscopy, providing an intuitive, molecule-centric explanation as to how SRS microscopy can outperform regular Raman microscopy. Hence, as unveiled by the new formulation, a duality of Raman scattering has emerged, with implications for both fundamental science and practical technology.
期刊介绍:
Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance.
Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.