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Critical Phenomena

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Critical Phenomena

The term critical phenomena is used synonymously with the term phase transitions. A phase transition involves a transformation of one phase to another and occurs at a characteristic temperature called a transition temperature or a critical temperature Tc. There are many different kinds of phase transitions such as fusion, vaporization and sublimation, as well as solid-solid, conducting-superconducting, and fluid-superfluid transitions. In systems undergoing phase transitions, the emergence of long-range order is seen in which the value of a physical quantity at an arbitrary point in the system is correlated with its value at a point a long distance away. A classification scheme of phase transitions was originally proposed by Paul Ehrenfest and is hence known as the Ehrenfest classification. Although several more elaborate classification schemes have been proposed, the one due to Ehrenfest is still the most popular. According to it, a transition for which the first derivative of the free energy with respect to temperature is discontinuous is called a first-order phase transition. The heat capacity, Cp , at a first-order transition is infinite. A second-order phase transition is one in which the first derivative of the thermodynamic potential with respect to temperature is continuous, but its second derivative is discontinuous. The heat capacity is discontinuous not infinite at the transition. Near a second order phase transition, due to the reduction of rigidity of the system, critical fluctuations dominate as their amplitude diverges when T Tc. A useful concept in analyzing phase transitions is that of a critical exponent. In general, if a physical quantity Q (T) either diverges or tends to a constant value (see Fig. 1) as T tends to Tc, it can be characterized by defining the reduced temperature as T Tc (1) Tc The associated critical exponent is found according to
ln Q ( ) 0 ln

= lim

(2)

Figure 1

The four generic behaviors near criticality.

The most important critical exponents are denoted as , , , , v and and describe the specific heat, order parameter, isothermal susceptibility, response to an external field, the correlation length and the pair correlation function, respectively (see Table 1).

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Critical Phenomena

Table 1 Exponent

The definitions of critical exponents for liquid-vapor and magnetic systems. Definition (liquid-vapor) specific heat at constant volume Definition (magnetic) specific heat at constant H CH ~ (-)- CH ~ - magnetization M ~ (-) isothermal susceptibility T ~ (-)- T ~ - magnetic field-magnetization H ~ |M| (T = Tc) correlation length ~ (-)- ~ - spin-spin pair correlation function (r) ~ |r|-(d-2+)

Cv ~ (-)- Cv ~ - density difference

L - G ~ (-) isothermal compressibility

T ~ (-)- T ~ - pressure-density critical isotherm

P - Pc ~ |L - G| (T = Tc) correlation length

v v

~ (-)- ~ - density-density pair correlation function

(r) ~ |r|-(d-2+)

The mean field approximation (Landau theory) describes the physics of phase transitions well except in the immediate vicinity of the critical point where order parameter fluctuations are enormous. It is assumed that close to Tc, the free energy F can be expanded in a Taylor series of the order parameter . Introducing the reduced temperature as a control parameter, the simplest such expansion is (see Fig. 2)

F (T , V , ) = F0 + a 2 + A4 4
where a > 0 and A4 > 0. Solving the equilibrium conditions for yields = 0 for > 0 and

(3)

a = 2A 4

1/ 2

for < 0

(4)

Figure 2

A prototype of second order phase transitions according to Landau.

NL2663 This gives = 0.5. Calculating the entropy

Critical Phenomena

S =

a2 F = S0 + T 2 A4 Tc

(5)

where for > 0, S = S0 is the entropy of the disordered phase gives the specific heat as

Cv = T

S a2 = C0 + T T 2 A4 Tc

(6)

where for > 0, Cv = C0 is the specific heat of the disordered phase. Hence, a discontinuity occurs at Tc (see Fig. 3). a2 C = . 2 A4 Tc Thus = 0.

(7)

Figure 3

Plots of S (T) and Cv (T) in the Landau model of a second order phase transitions.

Including in F an external field h coupled to

F = F0 + a 2 + A4 4 h .
and minimizing F with respect to yields an equation of state in the form

(8)

h = 2 a + 2 A4 2 .
Since the susceptibility
, we find h

(9)

= 2a + 12 A4 2

(10)

Since 0 as T Tc, the third exponent is = 1. At T = Tc the equation of state (9) simplifies to:

h 4 A4 3 ,

(11)

and hence ~ h1/3 giving = 3. The quartic expansion in the Landau model invariably leads to the classical critical exponents: = 0, = 0.5, = 1 and = 3. While the Landau theory cannot describe spatial fluctuations, following Ginzburg and Landaus proposal it can be extended to consider the free energy to be a functional:

r r F ( (r ), T ) = d 3 r A2 2 + A4 4 h + D( )2

(12)

where D describes the energy due to spatial inhomogeneities. Applying a variational principle to F results in a non-linear Klein-Gordon equation for the order parameter

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Critical Phenomena

h = 2 A2 + 4 A4 3 2 D 2 .
A linearized solution of (13) in spherical coordinates is

(13)

h0 e r / , 4D r

(14)

where ~ A-1 / 2 is the correlation length that diverges as T Tc so that the critical exponent = 0.5. Fourier 2 transforming the order parameter according to
r

(r ) L d / 2

k < k0

ke

rr ik r

(15)

where the cutoff wavelength k0 = -1 corresponds to the smallest periodicity, F becomes (for h=0)
F=

k < k0

(A
2 k

+ Dk 2 + L d

k , k ', k ''< k 0

A
4 * k

* * k ' k '' k + k ' k ''

(16)

Ignoring mode-mode coupling provides the basis for the Gaussian approximation where
F

k < k0

(A
2 k

+ Dk 2 .

(17)

The Fourier transform of the correlation function is found as

r r r r r r r (k ) = L d e ik ( r r ') < (r ) (r ' ) > dr dr ' = k

n A2 + Dk 2 2

(18)

Therefore, as T Tc we find that (k) ~ k-2 with = 0 in the Gaussian approximation. Hence (r) ~ r-(d - 2) where d is spatial dimensionality. The Gaussian approximation introduces a new value of the specific heat critical exponent =2-d/2. JACK A. TUSZYNSKI See also order parameters; ferromagnetism and ferroelectricity, nonlinear field equations

Further Reading Anderson, P.W. 1984. Basic Notions of Condensed Matter Physics. Menlo Park, California: Benjamin/Cummings Landau, L.D. and Lifshitz, E.M. 1959. Statistical Physics. London: Pergamon Ma, S.-K. 1976. Modern Theory of Critical Phenomena. New York: Benjamin Reichl, L.E. 1979. A Modern Course in Statistical Physics. Austin, Texas: Univ. of Texas Press Stanley, H.E. 1971. Introduction to Phase Transitions and Critical Phenomena. Oxford: Oxford University Press White, R.H. and Geballe, T. 1979. Long Range Order in Solids. New York: Academic Press Yeomans, J.M. 1992. Statistical Mechanics of Phase Transitions. Oxford: Oxford University Press