Residual entropy

Residual entropy is physically significant entropy, which is present even after a substance is cooled arbitrarily close to absolute zero. That is, if a material is reduced to its ground state, residual entropy occurs if the material can exist in multiple different ground states that have the same zero-point energy. Residual entropy tends to occur in substances which have very weak tendencies to align into their energy ground state. A common example is the case of carbon monoxide, which has a very small dipole moment. As the carbon monoxide crystal is cooled to absolute zero, few of the carbon monoxide molecules have enough time to align themselves into a perfect crystal, (with all of the carbon monoxide molecules oriented in the same direction). Because of this, the crystal is locked into a state with 2^N different corresponding microstates, giving a residual entropy of S = Nkln(2), rather than zero.

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History

One of the first examples of residual entropy was pointed out by Pauling to describe water ice. In water, each oxygen atom is bonded to two hydrogen atoms. However, when water freezes it forms a tetragonal structure where each oxygen atom has four hydrogen neighbors (due to neighboring water molecules). The hydrogen atoms sitting between the oxygen atoms have some degree of freedom as long as each oxygen atom has two hydrogen atoms that are 'nearby', thus forming the traditional H₂O water molecule. However, it turns out that for a large number of water molecules in this configuration, the hydrogen atoms have a large number of possible configurations that meet the 2-in 2-out rule (each oxygen atom must have two 'near' (or 'in') hydrogen atoms, and two far (or 'out') hydrogen atoms). This freedom exists down to absolute zero, which was previously seen as an absolute one-of-a-kind configuration. The existence of these multiple configurations that meet the rules of absolute zero amounts to randomness, or in other words, entropy. Thus systems that can take multiple configurations at or near absolute zero are said to have residual entropy.

Although water ice was the first material for which residual entropy was proposed, it is generally very difficult to prepare pure defect-free crystals of water ice for studying. A great deal of research has thus been undertaken into finding other systems that exhibit residual entropy. Geometrically frustrated systems in particular often exhibit residual entropy. An important example is spin ice, which is a geometrically frustrated magnetic material where the magnetic moments of the magnetic atoms have Ising-like magnetic spins and lie on the corners of network of corner-sharing tetrahedra. This material is thus analogous to water ice, with the exception that the spins on the corners of the tetrahedra can point into or out of the tetrahedra, thereby producing the same 2-in, 2-out rule as in water ice, and therefore the same residual entropy. One of the interesting properties of geometrically frustrated magnetic materials such as spin ice is that the level of residual entropy can be controlled by the application of an external magnetic field. This property can be used to create one-shot refrigeration systems.

See also

• Proton disorder in ice
• Geometrical frustration