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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 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 \cite{domb1996} and the historic early review by Fisher \cite{fisher1967}.
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 \cite{domb1965, widom1965, kadanoff1966,
patashinskii1966, griffiths1967}. 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 \cite{widom1964}
- (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 \cite{essam1963}
- (9)
When
the resulting
means, generally, a
logarithmic rather than power-law divergence together with a
superimposed finite discontinuity occurring between
and
\cite{widom1965}. 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 \cite{rice1955} and to Scott \cite{scott1953}. It was
before Domb and Sykes \cite{domb1957} and Fisher \cite{fisher1959} 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 \cite{guggenheim1945} 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 \cite{kadanoff1966, fisher1964}
- (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 (13),
vanishes
exponentially rapidly as
. Thus, from
(11) and from the earlier
we
have the scaling law \cite{fisher1964}
- (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 \cite{bwidom1965, watson1968}.
Exponents and the role of 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 \cite{bwidom1965}. With (15) we then have also \cite{bwidom1965}
- (17)
which, with (8) and (14), yields also \cite{stell1968}
- (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
.
Renormalization Group
This behavior is reflected again in the renormalization-group theory
\cite{wilson1971, kwilson1971, fisher1972}. 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 \cite{fisher1972}. 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
.
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 \cite{kadanoff1966}, which was itself one of the inspirations for the renormalization-group theory \cite{wilson1971, kwilson1971}.
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
i.e.,
is homogeneous of
degree
in
and
.
Then from the alternative form (2) of the property of
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 \cite{wilson1971, kwilson1971}.
References
[1] C. Domb, The Critical Point (Taylor and 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.

