Widom scaling

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Widom scaling (after Benjamin Widom) is a hypothesis in statistical mechanics regarding the free energy of a magnetic system near its critical point which leads to the critical exponents becoming no longer independent so that they can be parameterized in terms of two values. The hypothesis can be seen to arise as a natural consequence of the block-spin renormalization procedure, when the block size is chosen to be of the same size as the correlation length. [1]

Benjamin Widom is the Goldwin Smith Professor of Chemistry at Cornell University. His research interests include physical chemistry and statistical mechanics. In 1998, Widom was awarded the Boltzmann Medal "for his illuminating studies of the statistical mechanics of fluids and fluid mixtures and their interfacial properties, especially his clear and general formulation of scaling hypotheses for the equation of state and surface tensions of fluids near critical points."

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Thermodynamic free energy

The thermodynamic free energy is a concept useful in the thermodynamics of chemical or thermal processes in engineering and science. The change in the free energy is the maximum amount of work that a thermodynamic system can perform in a process at constant temperature, and its sign indicates whether a process is thermodynamically favorable or forbidden. Since free energy usually contains potential energy, it is not absolute but depends on the choice of a zero point. Therefore, only relative free energy values, or changes in free energy, are physically meaningful.

Contents

Widom scaling is an example of universality.

Definitions

The critical exponents and are defined in terms of the behaviour of the order parameters and response functions near the critical point as follows

, for
, for

where

measures the temperature relative to the critical point.

Near the critical point, Widom's scaling relation reads

.

where has an expansion

,

with being Wegner's exponent governing the approach to scaling.

Derivation

The scaling hypothesis is that near the critical point, the free energy , in dimensions, can be written as the sum of a slowly varying regular part and a singular part , with the singular part being a scaling function, i.e., a homogeneous function, so that

In mathematics, a homogeneous function is one with multiplicative scaling behaviour: if all its arguments are multiplied by a factor, then its value is multiplied by some power of this factor.

Then taking the partial derivative with respect to H and the form of M(t,H) gives

In mathematics, a partial derivative of a function of several variables is its derivative with respect to one of those variables, with the others held constant. Partial derivatives are used in vector calculus and differential geometry.

Setting and in the preceding equation yields

for

Comparing this with the definition of yields its value,

Similarly, putting and into the scaling relation for M yields

Hence


Applying the expression for the isothermal susceptibility in terms of M to the scaling relation yields

Setting H=0 and for (resp. for ) yields

Similarly for the expression for specific heat in terms of M to the scaling relation yields

Taking H=0 and for (or for yields

As a consequence of Widom scaling, not all critical exponents are independent but they can be parameterized by two numbers with the relations expressed as

The relations are experimentally well verified for magnetic systems and fluids.

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References

  1. Kerson Huang, Statistical Mechanics. John Wiley and Sons, 1987