Probing Two-Photon Properties of Molecules: Large Non-Condon Effects Dominate the Resonance Hyper-Raman Scattering of Rhodamine 6G.

Experimentally measured resonance hyper-Raman (RHR) spectra spanning the S ←S, S ← S, and S ← S transitions in rhodamine 6G (R6G) have been recorded. These spectra are compared to the results of first-principles calculations of the RHR intensity that include both Franck-Condon (A-term) and non-Condo...

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Published in:Journal of the American Chemical Society Vol. 133; no. 37; pp. 14590 - 14593
Main Authors: Milojevich, Chris B., Silverstein, Daniel W., Jensen, Lasse, Camden, Jon P.
Format: Article
Published: American Chemical Society 9/21/2011
Subjects:
Online Access:View this record in EBSCOhost
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      dt: 9/21/2011
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      pub: American Chemical Society
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        66701874
        10.1021/ja2054622
      ppf: 14590
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        atl: Probing Two-Photon Properties of Molecules: Large Non-Condon Effects Dominate the Resonance Hyper-Raman Scattering of Rhodamine 6G.
      aug:
        au:
          Milojevich, Chris B.
          Silverstein, Daniel W.
          Jensen, Lasse
          Camden, Jon P.
        affil:
          Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996-1600, United States
          Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802, United States
      su:
        Multiphoton processes
        Raman effect
        Mesomerism
        Franck-Condon principle
        Spectrum analysis
      sug:
        subj:
          Multiphoton processes
          Raman effect
          Mesomerism
          Franck-Condon principle
          Spectrum analysis
      ab: Experimentally measured resonance hyper-Raman (RHR) spectra spanning the S ←S, S ← S, and S ← S transitions in rhodamine 6G (R6G) have been recorded. These spectra are compared to the results of first-principles calculations of the RHR intensity that include both Franck-Condon (A-term) and non-Condon (B-term) scattering effects. Good agreement between the experimental and theoretical results is observed, demonstrating that first-principles calculations of hyper-Raman intensities are now possible for large molecules such as R6G. Such agreement indicates that RHR spectroscopy will now be a routine aid for probing multiphoton processes. This work further shows that optimization of molecular properties to enhance either A- or B-term scattering might yield molecules with significantly enhanced two-photon properties.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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          year: 2011
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