Raman bands explained
What do the Raman bands represent?
It is easy to understand the Raman spectrum of crystals with a regular array of identical atoms, all in the same configuration (such as the carbon atoms in diamond). In these cases, you often see just one dominant Raman band (because there is just one molecular environment of the crystal).
The Raman spectrum of polystyrene, however, is much more complex because the molecule is less symmetric and has hydrogen atoms in addition to carbon atoms. There are also different bond types connecting the atoms.
The frequencies of vibration depend on the masses of the atoms involved and the strength of the bonds between them. Heavy atoms and weak bonds have low Raman shifts. Light atoms and strong bonds have high Raman shifts.
We see the high frequency carbon-hydrogen (C-H) vibrations in the polystyrene spectrum at about 3000 cm-1. The low frequency carbon-carbon (C-C) vibrations are at around 800 cm-1. The C-H vibrations have a higher frequency than the C-C vibrations because hydrogen is lighter than carbon.
We see the vibrations of two carbon atoms linked by strong double bonds (C=C) at around 1600 cm-1. This is at a higher frequency than two carbon atoms lined by a weaker single bond (C-C, 800 cm-1).
You can use these simple rules to explain many of the features of Raman spectra.
Vibrations in detail
You can see more subtle effects if you inspect spectra closely. The strength of bonds also affects their vibration rates. For example, the C-H vibrations of polystyrene appear in two bands, at approximately 2900 cm-1 and 3050 cm-1. The carbons in the former are part of carbon chains ('aliphatic'), whereas the carbons in the latter form part of carbon rings ('aromatic').
You can view the vibrations of a complex molecule as partly consisting of many simple diatomic vibrations. However the full richness of the Raman spectrum can only be understood by considering the vibrations of larger groups of atoms (such as the expanding/contracting ‘breathing mode' of the aromatic carbon ring that appears at 1000 cm-1 in polystyrene).
Low frequency vibrations
You can also study Raman bands with low Raman shifts, below 100 cm-1. These originate from very heavy atoms or very large-scale vibrations, such as the whole crystal lattice vibrating. Renishaw's Raman instruments enable you to study these modes and explore a wide range of materials and crystals, and distinguish between different crystalline forms (polymorphs).
The big picture
A Raman spectrum therefore consists of a range of features, each associated with a vibrational mode. The spectrum is unique to the material and enables you to identify it. It is important to note that, although a full understanding of the vibrational modes is of interest, you rarely need this as you can use a reference database for identification.
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