Raman scattering differs fundamentally from fluorescence in scattering mechanisms
the verdict
INSUFFICIENT LEANING
refutedsupported
the weight of evidence
2 sources for · 0 against
The retrieved literature touches upon Raman scattering and fluorescence within spectroscopic contexts, but does not provide detailed proofs explaining their fundamental scattering mechanism differences.
The enhancements of normal Raman scattering, resonance Raman scattering, and fluorescence from molecules adsorbed on identical, well-characterized, silver-island films are reported. The enhancement arises from the electromagnetic interaction between the molecules and the electronic plasma resonance of the silver islands. A hierarchy of enhancement ratios is found, with typical values of 105 for RS, 103 for RRS and 10−1 to 10 for fluorescence, depending on the quantum yield of the molecular fluorescence. A model, developed on heuristic grounds and substantiated using the density matrix formalism, describes the light scattering processes and the effects of the plasma resonance. This model presents a unified picture of the surface-induced enhancement effects and is consistent with the experimental values. The comparison of all the forms of optical scattering leads to a complete determination of the role of the plasma resonances in the various portions of the scattering process. The excitation of the electronic plasma resonance results in an increased local field at the molecules leading to an increased excitation or absorption rate. Similarly, the excitation of the plasma resonance by the molecular emission dipole results in an increase in the radiative decay rate. However, the electromagnetic coupling of the molecule to the plasma resonance also adds an additional damping channel which can result in a reduction of the absorption or excitation rate as well as the emission yield. The resultant balance of these processes leads to the hierarchy in the measured enhancements. The hierarchy of enhancements is also shown to have important spectroscopic consequences.
A theory for the resonance light scattering in a molecular system interacting with the heat bath is developed, taking into account the multilevel structure of the molecular system. An expression for the cross section of the resonance light scattering process is derived by using the Liouville operator method in the Markoff approximation; the cross section consists of three terms: resonance Raman scattering, resonance fluorescence, and their mixing. The mixing term vanishes in the limit of the zero vibrational dephasing constant. Analytical expressions for the resonance Raman scattering and resonance fluorescence cross sections are derived in the displaced harmonic oscillator model. Model calculations of the vibrational band structure in the resonance light scattering cross section are performed by using the expressions derived. Differences of the band intensity distribution in the resonance fluorescence from that in the resonance Raman scattering are illustrated.
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