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4: InfraRed spectroscopy – looking at molecular vibrations

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    Up to now we have concentrated on the absorption (and emission) of energy caused by transitions of electrons between quantized energy levels. However, as we discussed earlier, electron energies are not the only quantized energies at the atomic- molecular level. In molecules, the energies of both molecular vibrations and rotations are also quantized, but the energies involved are much lower than those needed to break bonds. When two atoms are bonded, the atoms can move back and forth relative to each other: as they move, the potential energy of the two atom system changes (why is that?). There are also motions associated with rotations around bonds. But (weirdly, and quantum mechanically) rather than being able to assume any value, the energies of these vibrations (and rotations) are also quantized. The energy gaps between the vibrational energy levels tend to be in the range of infrared radiation. When we look at the light absorbed or emitted by vibrational energy changes we are doing what is known as infrared spectroscopy. Transitions from one rotational energy level to anther can be promoted by microwave radiation, leading to microwave spectroscopy. The table below provides examples of different types of spectroscopy, the wavelength of electromagnetic radiation typically involved, and the uses of each kind of spectroscopy.

    Table I

    Type of Spectroscopy

    Radiation wavelength

    Interaction with matter

    Purpose

    UV-VIS

    350-700 nm

    Electronic transitions in molecules

    Often used to determine concentrations

    IR

    2,500 to 16,000 nm

    Molecular vibrations

    To determine presence of particular groups of atoms (functional groups

    NMR

    10-100 m

    Nuclear transitions

    Identify types of C and H in molecules

    MRI

    10-100 m

    Nuclear transitions

    Imaging (typically human body parts)

    Why, you might ask, are we interested in the vibrations and rotations of molecules? It turns out that many molecules and fragments of molecules have very distinctive IR absorption patterns that can be used to identify them. The figure shows an IR spectrum of a carboxylic acid and how the various peaks can be ascribed to vibrations of different bonds or groups within the molecule. Infrared spectroscopy allows us to identify substances from these patterns, both in the lab and for example in interstellar dust clouds. The presence of quite complex molecules in space (hundreds of millions of light years away from earth) has been detected by the use of IR spectroscopy.

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