Scaling laws
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| Benjamin Widom (2009), Scholarpedia, 4(10):9054. | revision #69108 [link to/cite this article] | |||||||||||||||||||
Curator: Prof. Benjamin Widom, Cornell Univerity
Prof. Benjamin Widom accepted the invitation on 4 February 2009 (self-imposed deadline: 4 August 2009).
Scaling laws are the expression of physical principles in the mathematical language of homogeneous functions.
Contents |
Introduction
A function
is said to be homogeneous
of degree
in the variables
if, identically for all
,
- (1)
For example,
is homogeneous of degree 2 in
and
and of
the first degree in
and
.
By setting
in (1) we have
as an alternative expression of homogeneity:
is homogeneous of degree
in
if
- (2)
i.e., the
power of
times some
function
of the ratios
alone.
If
is homogeneous of degree
in
it satisfies Euler's
theorem :
- (3)
In thermodynamics, if the scale of a system is merely
increased by a factor
with no change in its
intensive properties, then all its extensive properties including its
entropy
, energy
, volume
,
and the masses
of each of its chemical
constituents are increased by that factor, so the extensive function
is homogeneous of degree 1 in
its extensive arguments:
- (4)
With
the temperature,
the
pressure, and
the chemical potential of the species
, we have the thermodynamic relations
,
,
and
; so from Euler's
theorem,
- (5)
an important identity. Any extensive function
, such as the volume V or the
Gibbs free energy
, is homogeneous of the first
degree in the
at fixed
and
, so
- (6)
an important class of relations.
Scaling laws
The foregoing are scaling relations in classical thermodynamics. In more recent times, in statistical mechanics, the expression "scaling laws" has been taken to refer to the homogeneity of form of the thermodynamic and correlation functions near critical points, and to the resulting relations among the exponents that occur in those functions. There are many excellent references for critical phenomena and the associated scaling laws, among them the superb book by Domb [1] and the historic early review by Fisher [2].
Near the Curie point (critical point) of a ferromagnet, which occurs
at
, the magnetic field
,
magnetization
, and
, are
related by
- (7)
where
is the "scaling" function
and
and
are two critical-point
exponents [3-7]. Thus, from (2) and (7),
as the critical point is approached
and
,
becomes a
homogeneous function of
and
of degree
. The scaling
function
vanishes proportionally to
as
approaches
, with
a
positive constant; it diverges proportionally to
as
;
and
, another positive constant (Fig. 1).
Although (7) is confined to the immediate neighborhood
of the critical point
all near 0), the scaling
variable
nevertheless
traverses the infinite range
.
When
and
, so that
is then the spontaneous magnetization, we have from
(7),
,
where
is the conventional symbol for this
critical-point exponent. When
on the
critical isotherm
, we have
, where
is the
conventional symbol for this exponent. From the first of the two
properties of
noted above, and Eq.(7),
one may calculate the magnetic susceptibility
, which is then seen to diverge proportionally
to
, both at
with
and at
with
(although with different coefficients). The
conventional symbol for the susceptibility exponent is
, so we have [8]
- (8)
Equations (7) and (8) are examples of scaling laws, Eq.(7) being a statement of homogeneity and the exponent relation (8) a consequence of that homogeneity.
A free energy
may be obtained from (7) by
integrating at fixed temperature, since
, and the corresponding heat capacity
then follows from
. One then finds from (7) that
at
diverges at the critical point
proportionally to
(with different
coefficients for
and
, with the critical-point exponent
related to
and
by the scaling
law [9]
- (9)
When
the resulting
means, generally, a logarithmic rather than power-law divergence
together with a superimposed finite discontinuity occurring between
and
[4]. In the
2-dimensional Ising model the discontinuity is absent and only the
logarithm remains, while in mean-field (van der Waals, Curie-Weiss,
Bragg-Williams) approximation the logarithm is absent but the
discontinuity is still present.
Critical exponents
What were probably the historically earliest versions of
critical-point exponent relations like (8) and
(9) are due to Rice [10] and to Scott [11].
It was before Domb and Sykes [12] and
Fisher [13] had noted that the exponent
was in reality greater than its mean-field value
but when it was already clear from Guggenheim's
corresponding-states analysis [14] that
had a value much closer to 1/3 than to its
mean-field value of 1/2. Then, under the assumption
and
, Rice had concluded from
the equivalent of (8) that
(the correct value is now known to be closer to 5) and
Scott had concluded from the equivalent of (9) that
(the correct value is now
known to be closer to 1/10). The mean-field values are
and (as noted above)
.
The long-range spatial correlation functions in ferromagnets and
fluids also exhibit a homogeneity of form near the critical point. At
magnetic field
(assumed for simplicity) the
correlation function
as a function of the spatial
separation
(assumed very large) and temperature near
the critical point (t assumed very small), is of the form [5,15]
- (10)
Here
is the
dimensionality of space,
is another critical-point
exponent, and
is the correlation length (exponential
decay length of the correlations), which diverges as
- (11)
as the critical point is
approached, with
still another critical-point
exponent. Thus,
(with
is a
homogeneous function of
and
of degree
. The scaling
function
has the properties (to within constant
factors of proportionality),
- (12)
Thus, as
in any fixed thermodynamic state
(fixed t) near the critical point,
decays with
increasing
proportionally to
, as in the
Ornstein-Zernike theory. If, instead, the critical point is
approached
with a fixed, large
, we have
decaying with
only as an inverse power,
, which corrects
the
that appears in the Ornstein-Zernike
theory in that limit. The scaling law (10) with scaling
function
interpolates between these extremes.
In the language of fluids, with
the number density
and
the isothermal compressibility, we have as an
exact relation in the Ornstein-Zernike theory
- (13)
with
Boltzmann's constant and where the integral is over all space with
the element of volume. The same relation holds in
the ferromagnets with
then the magnetic
susceptibility and with the deviation of
from the
critical density
then the magnetization
. At the critical point
is infinite
and correspondingly the integral diverges because the decay length
is then also infinite. The density
is there just the finite positive constant
and
the finite
. Then from the scaling law
(10), because of the homogeneity of
and because the main contribution to the diverging integral comes from
large
, where (10) holds, it follows that
diverges proportionally to 
. But the integral is now
finite because, by (12),
vanishes
exponentially rapidly as
. Thus, from
(11) and from the earlier
we have the scaling law [15]
- (14)
The surface tension
in liquid-vapor equilibrium,
or the analogous excess free energy per unit area of the interface
between coexisting, oppositely magnetized domains, vanishes at the
critical point (Curie point) proportionally to
with
another critical-point exponent. The
interfacial region has a thickness of the order of the correlation
length
so
is the free energy
per unit volume associated with the interfacial region. That is in
its magnitude and in its singular critical-point behavior the same
free energy per unit volume as in the bulk phases, from which the heat
capacity follows by two differentiations with respect to the
temperature. Thus,
vanishes proportionally to
; so, together with (9),
- (15)
another scaling relation [16,17].
Exponents and space dimension
The critical-point exponents depend on the dimensionality
. The theory was found to be illuminated by treating
as continuously variable and of any magnitude. There
is a class of critical-point exponent relations, often referred to as
hyperscaling, in which
appears explicitly. The
correlation length
is the coherence length of density
or magnetization fluctuations. What determines its magnitude is that
the excess free energy associated with the spontaneous fluctuations in
the volume
must be of order
, which
has the finite value
at the critical point. But the
typical fluctuations that occur in such an elemental volume are just
such as to produce the conjugate phase. The free energy
is then that for creating an interface of area
, which is
. Thus,
as the critical point is approached
has
a finite limit of order
. Then from the definitions
of the exponents
and
,
- (16)
a hyperscaling relation [16]. With (15) we then have also [16]
- (17)
which, with (8) and (14), yields also [18]
- (18)
Unlike the scaling laws (8), (9),
(14), and (15), which make no explicit
reference to the dimensionality, the
-dependent exponent
relations (16)-(18) hold only for
. At
the exponents assume the values
they have in the mean-field theories but logarithmic factors are then
appended to the simple power laws. Then for
, the
terms in the thermodynamic functions and correlation-function
parameters that have as their exponents those given by the mean-field
theories are the leading terms. The terms with the original
-dependent exponents, which for
were
the leading terms, have been overtaken, and, while still present, are
now sub-dominant.
This progression in critical-point properties from
to
to
is seen clearly in the phase
transition that occurs in the analytically soluble model of the ideal
Bose gas. There is no phase transition or critical point in it for
. When
the chemical potential
(not to be confused with the surface-tension exponent
) vanishes identically for all
, where
is the density,
is the thermal de Broglie wavelength
with
Planck's constant
and
the mass of the atom, and
is
the Riemann zeta function. As
from below,
vanishes through a
range of negative values. As
, the
difference
vanishes (to within
positive proportionality factors) as
- (19)
When
the mean-field
is
still present but is dominated by
; when
the singular
is still
present but is dominated by the mean-field
.
This behavior is reflected again in the renormalization-group theory
[19-21]. In the simplest cases there are two competing fixed points for
the renormalization-group flows, one of them associated with
-dependent
exponents that satisfy both the
-independent scaling relations and
the hyperscaling relations, the other with the
-independent
exponents of the mean-field theories [21]. The first determines the leading
critical-point behavior when
. At
the two fixed
points coincide and the exponents are now those of the mean-field
theories but with logarithmic factors appended to the mean-field power
laws. For
the two fixed points separate again and
the leading critical-point behavior now comes from the one whose
exponents are those of the mean-field theories. The effects of both
fixed points are present at all
, but the dominant
critical-point behavior comes from only the one or the other,
depending on
.
Origin of homogeneity; block spins
A physical explanation for the homogeneity in (7) and (10) and for the exponent relations that are consequences of them is provided by the Kadanoff block-spin picture [5], which was itself one of the inspirations for the renormalization-group theory [19,20].
In a lattice spin model (Ising model), one considers blocks of spins,
each of linear size
, thus containing
spins, with
much less than the diverging correlation
length
(Fig. 2).
Each block interacts with its neighbors through their common boundary
as though it were a single spin in a re-scaled model. Each block is
of finite size so the spins in its interior contribute only analytic
terms to the free energy of the system. The part of the free-energy
density (free energy per spin) that carries the critical-point
singularities and their exponents comes from the interactions between
blocks. Let this free-energy density be
, a
function of temperature through
and of the
magnetic field
. The correlation length is the same in
the re-scaled picture as in the original, but measured as a number of
lattice spacings it is smaller in the former by the factor
. Thus, the re-scaled model is effectively further from
its critical point than the original was from its; so with
and
both going to 0 as the critical
point is approached, the effective
and
in the re-scaled model are
and
with positive exponents
and
, so
increasing with
. From the point of view of the
original model the contribution to the singular part of the free
energy made by the spins in each block is
,
while that same quantity, from the point of the view of the re-scaled
model, is
. Thus,
- (20)
i.e., by (1),
is a homogeneous function of
and
of degree
.
Therefore, by (2),
where
and
are functions only of the ratio
. At
the first of these gives
. But two temperature derivatives
of
gives the contribution to the heat capacity per
spin, diverging as
; so
. Also, on the critical isotherm
, the second relation above gives
. But the magnetization per spin is
, vanishing as
, so
. The exponents
and
have thus been identified in
terms of the thermodynamic exponents: the heat-capacity exponent
and the critical-isotherm exponent
. In the meantime, again with
the magnetization per spin, the homogeneity of
form of
in (20) is equivalent to
that of
in (7), from which the
scaling laws
and
are known to follow.
A related argument yields the scaling law (10) for the
correlation function
, with
again
for simplicity. In the re-scaled model,
becomes
, as before, while
becomes
. There may also be a factor, say
with some exponent
, relating the magnitudes of the
original and rescaled functions; thus,
- (21)
i.e.,
is homogeneous of
degree
in
and
.
Then from the alternative form (2) of the property of
homogeneity,
- (22)
with
a scaling function
. Comparing this with
(10), and recalling that the correlation length
diverges at the critical point as
with exponent
, we identify
and
. The scaling law
, which was a consequence of the
homogeneity of form of
, again holds, while from
and the earlier
we now
have the hyperscaling law (17),
.
The block-spin picture thus yields the critical-point scaling of the
thermodynamic and correlation functions, and both the
-independent and
-dependent relations
among the scaling exponents. The essence of this picture is confirmed
in the renormalization-group theory [19,20].
References
[1] C. Domb, The Critical Point (Taylor & Francis, 1996).
[2] M.E. Fisher, Repts. Prog. Phys. 30, part 2 (1967) 615.
[3] C. Domb and D.L. Hunter, Proc. Phys. Soc. 86 (1965) 1147.
[4] B. Widom, J. Chem. Phys. 43 (1965) 3898.
[5] L.P. Kadanoff, Physics 2 (1966) 263.
[6] A.Z. Patashinskii and V.L. Pokrovskii, Soviet Physics JETP 23 (1966) 292.
[7] R.B. Griffiths, Phys. Rev. 158 (1967) 176.
[8] B. Widom, J. Chem. Phys. 41 (1964) 1633.
[9] J.W. Essam and M.E. Fisher, J. Chem. Phys. 38 (1963) 802.
[10] O.K. Rice, J. Chem. Phys. 23 (1955) 169.
[11] R.L. Scott, J. Chem. Phys. 21 (1953) 209.
[12] C. Domb and M.F. Sykes, Proc. Roy. Soc. A 240 (1957) 214.
[13] M.E. Fisher, Physica 25 (1959) 521.
[14] E.A. Guggenheim, J. Chem. Phys. 13 (1945) 253.
[15] M.E. Fisher, J. Math. Phys. 5 (1964) 944.
[16] B. Widom, J. Chem. Phys. 43 (1965) 3892.
[17] P.G. Watson, J. Phys. C1 (1968) 268.
[18] G. Stell, Phys. Rev. Lett. 20 (1968) 533.
[19] K.G. Wilson, Phys. Rev. B 4 (1971) 3174.
[20] K.G. Wilson, Phys. Rev. B 4 (1971) 3184.
[21] K.G. Wilson and M.E. Fisher, Phys. Rev. Lett. 28 (1972) 240.
Internal references
- Tomasz Downarowicz (2007) Entropy. Scholarpedia, 2(11):3901.
- Eugene M. Izhikevich (2007) Equilibrium. Scholarpedia, 2(10):2014.
- Giovanni Gallavotti (2008) Fluctuations. Scholarpedia, 3(6):5893.
- Cesar A. Hidalgo R. and Albert-Laszlo Barabasi (2008) Scale-free networks. Scholarpedia, 3(1):1716.
See also
| Benjamin Widom (2009) Scaling laws. Scholarpedia, 4(10):9054, (go to the first approved version) Created: 2 February 2009, reviewed: 20 October 2009, accepted: 20 October 2009 |


