What Is Vibrational Raman Spectroscopy: A Vibrational or an Electronic Spectroscopic Technique or Both?

Abstract

Modern Raman spectroscopy covers several noninvasive reflection techniques for identification of molecules and investigation of molecular properties. All are based on the Raman effect, occurring when polarized laser light is inelastically scattered by a molecular sample. Vibrational Raman spectroscopy is the Raman technique most widely used in chemical analysis, and it is relevant for the characterization of molecules in solution, biomolecules, and solids (crystals and powders). In this chapter vibrational Raman spectroscopy is discussed under the headline: “What is vibrational Raman spectroscopy: a vibrational or an electronic spectroscopic technique, or both?” The answer to this question is gained through a discussion of different scattering situations, and it is demonstrated that the Raman technique is more than an alternative technique to infrared and near-infrared absorption spectroscopy. Starting with the Kramers-Heisenberg equation, the answer is obtained through a discussion of: State tensors and Raman tensors, nonresonance and resonance Raman scattering (RRS) excited with a single laser wavelength, and unpolarized and polarization-resolved RRS excited with variable laser wavelengths (RADIS), dispersive Raman vibrations as a tool for noninvasive detection of molecular color changes and that RADIS data are automatically born as three-dimensional multivariate data with high information contents.