Infrared spectroscopy

Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) involves the interaction of infrared radiation with matter. It covers a range of techniques, mostly based on absorption spectroscopy. As with all spectroscopic techniques, it can be used to identify and study chemicals. Samples may be solid, liquid, or gas. The method or technique of infrared spectroscopy is conducted with an instrument called an infrared spectrometer (or spectrophotometer) to produce an infrared spectrum. An IR spectrum can be visualized in a graph of infrared light absorbance (or transmittance) on the vertical axis vs. frequency or wavelength on the horizontal axis. Typical units of frequency used in IR spectra are reciprocal centimeters (sometimes called wave numbers), with the symbol cm−1. Units of IR wavelength are commonly given in micrometers (formerly called "microns"), symbol μm, which are related to wave numbers in a reciprocal way. A common laboratory instrument that uses this technique is a Fourier transform infrared (FTIR) spectrometer. Two-dimensional IR is also possible as discussed below.

The infrared portion of the electromagnetic spectrum is usually divided into three regions; the near-, mid- and far- infrared, named for their relation to the visible spectrum. The higher-energy near-IR, approximately 14000–4000 cm−1 (0.8–2.5 μm wavelength) can excite overtone or harmonic vibrations. The mid-infrared, approximately 4000–400 cm−1 (2.5–25 μm) may be used to study the fundamental vibrations and associated rotational-vibrational structure. The far-infrared, approximately 400–10 cm−1 (25–1000 μm), lying adjacent to the microwave region, has low energy and may be used for rotational spectroscopy. The names and classifications of these subregions are conventions, and are only loosely based on the relative molecular or electromagnetic properties.

Infrared spectroscopy exploits the fact that molecules absorb frequencies that are characteristic of their structure. These absorptions occur at resonant frequencies, i.e. the frequency of the absorbed radiation matches the vibrational frequency. The energies are affected by the shape of the molecular potential energy surfaces, the masses of the atoms, and the associated vibronic coupling.

In particular, in the Born–Oppenheimer and harmonic approximations, i.e. when the molecular Hamiltonian corresponding to the electronic ground state can be approximated by a harmonic oscillator in the neighborhood of the equilibrium molecular geometry, the resonant frequencies are associated with the normal modes corresponding to the molecular electronic ground state potential energy surface. The resonant frequencies are also related to the strength of the bond and the mass of the atoms at either end of it. Thus, the frequency of the vibrations are associated with a particular normal mode of motion and a particular bond type.

In order for a vibrational mode in a sample to be "IR active", it must be associated with changes in the dipole moment. A permanent dipole is not necessary, as the rule requires only a change in dipole moment.

A molecule can vibrate in many ways, and each way is called a vibrational mode. For molecules with N number of atoms, linear molecules have 3N – 5 degrees of vibrational modes, whereas nonlinear molecules have 3N – 6 degrees of vibrational modes (also called vibrational degrees of freedom). As an example H2O, a non-linear molecule, will have 3 × 3 – 6 = 3 degrees of vibrational freedom, or modes.

This page was last edited on 12 May 2018, at 02:47.
Reference: https://en.wikipedia.org/wiki/Infrared_spectroscopy under CC BY-SA license.

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