Motional narrowing
Encyclopedia
In physics
Physics
Physics is a natural science that involves the study of matter and its motion through spacetime, along with related concepts such as energy and force. More broadly, it is the general analysis of nature, conducted in order to understand how the universe behaves.Physics is one of the oldest academic...

 and chemistry
Chemistry
Chemistry is the science of matter, especially its chemical reactions, but also its composition, structure and properties. Chemistry is concerned with atoms and their interactions with other atoms, and particularly with the properties of chemical bonds....

, motional narrowing is a phenomenon where a certain resonant frequency has a smaller linewidth than might be expected, due to motion in an inhomogeneous system.

Example: NMR spectroscopy

A common example is NMR
Nuclear magnetic resonance
Nuclear magnetic resonance is a physical phenomenon in which magnetic nuclei in a magnetic field absorb and re-emit electromagnetic radiation...

. In this process, the nuclear spin of an atom starts rotating, with the frequency of rotation proportional to the external magnetic field that the atom experiences. However, in an inhomogeneous medium, the magnetic field often varies from point to point (depending, for example, on the magnetic susceptibility of nearby atoms), so the frequency of nuclear spin rotation is different in different places. Therefore, when detecting the resonant rotation frequency, there is a linewidth (i.e., finite range of different frequencies) due to the variation in that resonant frequency from point to point. (This is called "inhomogeneous broadening".)

However, if the atoms are diffusing
Diffusion
Molecular diffusion, often called simply diffusion, is the thermal motion of all particles at temperatures above absolute zero. The rate of this movement is a function of temperature, viscosity of the fluid and the size of the particles...

 around the system, they will experience a higher magnetic field than average sometimes, and a lower magnetic field than average other times. Therefore, (in accordance with the central limit theorem
Central limit theorem
In probability theory, the central limit theorem states conditions under which the mean of a sufficiently large number of independent random variables, each with finite mean and variance, will be approximately normally distributed. The central limit theorem has a number of variants. In its common...

), the time-averaged magnetic field experienced by an atom has less variation than the instantaneous magnetic field does. As a consequence, when detecting the resonant rotation frequency, the linewidth is smaller (narrower) than it would be if the atoms were stationary. This is the motional narrowing effect.

Example: Vibrational spectroscopy

A similar phenomenon occurs in many other systems. Another example is vibrational modes in a liquid. Each molecule of the liquid has vibrational modes, and the vibrational frequency is influenced by the positions of nearby molecules. However, if the nearby molecules reorient and move around fast enough, the vibration will essentially occur at an averaged frequency, and therefore have a smaller linewidth. For example, simulations suggest that the OH stretch vibration linewidth in liquid water is 30% smaller than it would be without this motional narrowing effect.
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