Abstract
The goal of this chapter is to provide a general introduction to the principles of Raman spectroscopy. The chapter will therefore begin with a theoretical description of the Raman effect i.e. the classical electrodynamic treatment of Raman scattering, the discussion of the Raman intensities and the quantum mechanical picture. Enhancement mechanisms for Raman Microscopy will be discussed in the second part and resonant Raman as well as surface-enhanced Raman spectroscopy will then be explained in detail.
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Notes
- 1.
As in all practical modern applications of Raman scattering a laser is used as the excitation light source, the terms excitation light and laser light as well as excitation frequency, \(\omega _0\) and laser frequency are used synonymously.
- 2.
We note that \(\mu \) and E are vector quantities, while \(\alpha \) represents a 3rd rank tensor. Keeping this in mind, vector notation is dropped from now on.
- 3.
In the derivation presented here, molecular rotations are neglected as classical theory does not yield discrete excitation energies for molecular rotations.
- 4.
This is different for a hetero-diatomic molecule, which has a permanent dipole moment, whose derivative at the equilibrium position is non-zero.
- 5.
For the derivation of a quantitative expression of the polarizability tensor the reader is referred to the section on the quantum mechanical picture of Raman scattering.
- 6.
It can be shown (see S. Mukamel, Principles of Nonlinear Optics and Spectroscopy, Oxford University Press (1995)), that in the case of no dephasing of the excited-state wavefunction RR scattering and fluorescence are identical. In the - in most experimental situations realistic - case of dephasing being present RR scattering is associated with the emission of the initial coherent excited-state wavefunction prior to dephasing, while fluorescence reflects the emission of the incoherent wavefunction after dephasing.
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Dietzek, B., Cialla, D., Schmitt, M., Popp, J. (2018). Introduction to the Fundamentals of Raman Spectroscopy. In: Toporski, J., Dieing, T., Hollricher, O. (eds) Confocal Raman Microscopy. Springer Series in Surface Sciences, vol 66. Springer, Cham. https://doi.org/10.1007/978-3-319-75380-5_3
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