8 Curvature and fluctuations

8.1 Fluctuations of interfaces and capillary waves

The description of the fluid–fluid interface in section 7.3 was restricted to pla-
nar interfaces, with a density profile depending only on one coordinate. This
restriction to a special family of density profiles is characteristic of a mean field
approach. An actual interface, however, is a fluctuating object. In fact, in the ab-
sence of any external field, the position of the interface can fluctuate throughout
the accessible volume, so that the average density is, in principle, uniform! The
density functional approach, being essentially a mean field one, is not appropriate
for treating these fluctuations. A complete treatment, starting from a microscopic
description of the system, is equally hopeless. The physical solution consists in
using a coarse grained approach, in which the phase space of the system is re-
duced to the large wavelength coordinates that define the position of a weakly
curved interface. The energy of this weakly curved interface is of the form



Hcap = γ d2 A (8.1)

where d2 A is the element of area of the interface, and γ is the surface tension for
a planar interface, calculated e.g. using the theory of section 7.3. The ‘energy’ in
equation (8.1), also known as a ‘capillary Hamiltonian’ is actually a free energy,
as indicated by the presence of the surface tension γ , which depends on thermo-
dynamic parameters like the temperature. This effective Hamiltonian therefore
includes fluctuations of short (molecular) wavelength, which are embedded in
the definition of γ . The total free energy of the system is obtained by integrat-
ing the Boltzmann weight exp(−Hcap /kB T ) over a phase space defined by the
possible positions of the interface.
The calculation can be carried out if one restricts the phase space inte-
gration to those configurations that deviate only weakly from the planar con-
figuration. As discussed in section 6.2, such interfaces can  be described by
a function h(x, y), and the element of area is d A = dxdy 1 + h 2x + h 2y 
2

dxdy (1 + h 2x /2 + h 2y /2). The capillary Hamiltonian is most easily expressed

213

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 214 Curvature and fluctuations

by introducing the Fourier representation for a system of size L × L

1 
h(q) = d2 Rh(R) exp(iq · R) h(R) = h(q) exp(−iq · R) (8.2)
L2 q

where R = (x, y) and q = (qx , q y ) are two-dimensional vectors. With this nota-
tion, the capillary Hamiltonian can be rewritten (up to an extensive constant γ A)
as
γ  2
Hcap = q |h(q)|2 (8.3)
2L 2 q

and the partition function is expressed as an integral over the complex Fourier
components h(q)

  
γ 
Q= d h(q) exp −
2
q2 |h(q)|2 (8.4)
q
2kB T L 2 q

This partition function is a simple Gaussian integral, so that averages can be

easily expressed. One finds
2kB T L 2
|h(q)|2 = (8.5)
γ q2
and
kB T  −2
|h(R)|2 = q (8.6)
γ L2 q

The sum over wavevectors can be transformed into an integral, using the identity,
valid for large systems,


1  1
= d2 q (8.7)
L2 q (2π)2

The lower bound in the integral is qmin = 2π/L, determined by the system size.
The upper bound can be taken to be qmax = 2π/ξ , where ξ is the interfacial width
(see section 7.3) below which the coarse-grained description does not hold any
more. Equation (8.6) then yields

qmax  
kB T 2πqdq kB T L
|h(R)|2 = = ln (8.8)
4π2 γ qmin q2 2πγ ξ
Equation (8.8) indicates that the effective width of the interface, when the fluctua-
tions are included, is actually a divergent quantity. The average width, as measured
by equation (8.8), increases logarithmically with system size. Although such a
divergence may seem alarming at first sight, there are several reasons why it is
not very important in practice. The first one is related to the weakness of the
logarithmic divergence. A simple numerical application shows that even for an
interface of one square kilometer, the width defined by (8.8) would not exceed
a few nanometres. The second reason is that gravity will actually introduce a

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 8.2 Membranes and curvature moduli 215

cut-off at a wavevector qg much larger than 2π/L, as shown in the following

exercise.

Exercise: The liquid and the vapour have different densities. If ρ is the mass
density difference, show that for a gravity field g along the z axis, the gravitational
energy of the curved interface can be expressed as



gρ
dx dy h(x, y)2 (8.9)
2
Show next that
2kB T L 2
|h(q)|2 = (8.10)
γ (q 2 + −2 )
√
where  = γ /gρ is the capillary length, i.e. the length scale above which
gravity effects become dominant over capillary ones.
Deduce from (8.10) that for L  
 
kB T 
|h(R)|2 = ln (8.11)
2πγ ξ
so that the interfacial width due to fluctuations is not divergent.

The surface fluctuations described in this section are usually termed capillary
waves, in reference to their dynamical behaviour. A fluctuation of the interface
with wavevector q is a collective mode in the sense discussed in section 11.5,
with a dispersion relation that can be computed from hydrodynamics 1 . These
collective modes have been studied in light-scattering experiments 2 similar to
the neutron-scattering experiments described in section 11.6.

8.2 Membranes and curvature moduli

Fluid membranes are two-dimensional objects made of surfactant, or amphiphilic
molecules, which tend, for high enough concentrations, to self-assemble in such a
way as to minimize the amount of molecules exposed to an unfavourable solvent
(see section 2.6). Membranes may be of the monolayer type, separating two
different solvents, or bilayers separating similar solvents (figure 2.4). We will
consider in the following the case of amphiphiles that are highly insoluble, so
that the fraction of solvated molecules is essentially negligible. In this case,
adding more surfactant molecules to the system results in an increase of the area

1See e.g. L. Landau and E. Lifshitz, Hydrodynamics, Pergamon Press, Oxford, 1959.
2J. Charvolin, J-F. Joanny and J. Zinn-Justin (eds.), Liquids at Interfaces, North Holland,
Amsterdam, 1990.

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 216 Curvature and fluctuations

of the membranes contained in the system. Under these conditions, it turns out
that the interfacial tension associated with the membranes is effectively zero.
This somewhat surprising result can be understood as follows. The number of
surfactant molecules per unit area in a membrane, , is a free parameter, which
will adjust in such a way as to minimize the free energy of the system. If f (, T )
is the free energy per unit area of a membrane with surface density , one has at
equilibrium,
∂ f (, T )
=0 (8.12)
∂
Increasing the membrane area at fixed number of molecules is equivalent to
modifying . Equation (8.12) indicates that the free energy cost of this operation,
which defines the surface tension of the membrane, actually vanishes.
When the surface tension vanishes, the surface free energy is dominated by
terms that involve higher order contributions in terms of the deviation from a
planar shape. These deviations are characterized by the curvatures of the surface,
defined in section 6.2. The lowest order contributions from these curvatures to
the free energy can be written in the generic form


1

Fcurv = d2 A κ(H − H0 )2 + κ̄ K (8.13)

2
where H and K are the curvatures introduced in section 6.2. This free energy
depends on three parameters characteristic of the membrane, κ, H0 and κ̄. H0
describes the spontaneous curvature of the membrane. In a monolayer, the tail
and head of the amphiphilic molecule generally have different volumes, so that
the membrane will spontaneously bend in such a way as to optimize the global
packing (figure 2.4). H0 , however, vanishes in bilayers for symmetry reasons.
The curvature moduli κ and κ̄ are known as the bending and splay moduli,
respectively. κ quantifies the energy penalty associated with a deviation of the
mean curvature from its ‘natural’ value H0 . κ̄, in contrast, describes the penalty
associated with the formation of saddle-points in the surface. Typical values of
κ and κ̄ for phospholipidic membranes are in the range (1–100)kB T at room
temperature, so that thermal fluctuations are often essential.
The nature of the fluctuations in systems governed by the free energy (8.13)
will be considered in the next section. Before we do so, let us mention the special
behaviour of the splay term in equation (8.13). The so-called Gauss–Bonnet
theorem specifies that for a surface of fixed topology, this term is a constant that
depends only on the topology and not on the shape of the surface. Specifically,
one has


K d2 A = 4π(1 − g) (8.14)

where g is the genus of the surface, i.e. the number of holes in the surface: g = 0
for a sphere, g = 1 for a torus. The equality (8.14) stems from the fact that the

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 8.3 Fluctuations of membranes 217

integrand, K d2 A, is invariant under a transformation that maps a surface onto

a topologically equivalent one (e.g. a sphere onto an ellipsoid). The important
implication is that, unless one wants to compare the free energies of topologically
different surfaces, the saddle-splay term can be ignored.

8.3 Fluctuations of membranes

For a weakly curved bilayer (H0 = 0), described by a function h(x, y), the cur-
vature free energy (8.13) can be written in the form



κ κ  4
Fcurv = dx dy (∇2 h)2 = q |h(q)|2 (8.15)
2 2L 2 q

where, as in section 8.1, we have used equation (6.13) for H , and the Fourier
representation of the function h(x, y) for a system of size L × L. The term
involving the Gaussian curvature has been ignored, since we are interested in
fluctuations that affect only the shape of the membrane, leaving its topology
unchanged.
As in section 8.1, the free energy (8.15) will be considered as an effec-
tive Hamiltonian for the long wavelength fluctuations, assuming all contribu-
tions from short-range correlations have been lumped into the definition of
the curvature moduli. As for the area fluctuations described by the capillary
Hamiltonian (8.3), the statistics of the membrane fluctuations described by the
Hamiltonian (8.15) is Gaussian and one may write, in analogy with equations
(8.4), (8.5), and (8.6)

2kB T L 2
|h(q)|2 = (8.16)
κq 4

and
 2
kB T  −4 kB T L
|h(R)|2 = q  (8.17)
κ L2 q πκ 2π

where the lower cut-off q = 2π/L has once again been used. Equation (8.17)
shows that the fluctuations have a very strong effect on the position of the mem-
brane. The uncertainty in the vertical coordinate is proportional to the in-plane
dimension. A membrane is a much ‘softer’ and strongly fluctuating object than
an interface with non-zero surface tension. Clearly this makes the description
as a weakly undulated interface questionable for large membranes. In order to
estimate the length scale at which fluctuations become dominant, we compute
the average deviation of the normal to the membrane from the z direction. The
normal N(x, y) has coordinates (h x , h y , 1) (see section 6.2) so that the mean

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 218 Curvature and fluctuations

squared deviation is given by

  
−4 kB T L
(N(x, y) − ez ) = L
2
q |h(q)| 
2 2
ln (8.18)
q
2πκ ξ

where the large q cut-off, determined by the membrane width, is equal to 2π/ξ .
From equation (8.18) we deduce that the membrane will appreciably deviate from
the x y plane as soon as its dimension exceeds the persistence length
 
2πκ
ξp = ξ exp (8.19)
kB T

Gravity, which acted as a cut-off mechanism for fluctuations of interfaces, is

generally irrelevant in membrane systems, which are often symmetric (bilayers).
Therefore systems containing many membranes will be dominated by fluctuation
effects. In the next section we discuss, as an example, the steric interactions
between membranes generated by these fluctuations.

8.4 Steric interactions between membranes

Systems containing a large amount of membranes tend to display a large scale
(mesoscopic) organization. In a large fraction of the phase diagram, this organi-
zation takes the form of lamellar phases, i.e. a periodic stacking of membranes
perpendicularly to a fixed direction. The spatial period of this arrangement is
determined by the various interactions between membranes, which may be of
the van der Waals or electrostatic type, but also include a confinement interac-
tion known as the Helfrich interaction. Physically, this interaction comes from
the entropy reduction of a membrane confined by its neighbours in the stack.
This entropy penalty can be calculated as follows. Let d be the distance between
membranes in the stack. According to (8.17), the confinement will be felt by a
membrane when its size reaches L d such that
 2
kB T Ld
= d2 (8.20)
πκ 2π

In order to compute the free energy of a given membrane, we will assume that it
can be divided into blocks of lateral size L d × L d , each block being unaffected by
the interactions between membranes. The free energy of a block can be computed
from the curvature free energy (8.15). For simplicity, we satisfy ourselves with
an order of magnitude estimate, replacing (∇2 h) in equation (8.15) by d/L 2d .
Within this rough approximation, the free energy of a block is
 2
d
F(L d , d)  κ L 2d (8.21)
L 2d

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 Further reading 219

and the total free energy for a membrane of size L × L is obtained by adding the
contributions from different blocks of size L d × L d as
(kB T )2
F(L , d)  L 2 (8.22)
κd 2
This free energy corresponds to a repulsive interaction between the membranes,
that varies as the inverse square of their distance. When combined with the other
types of interactions listed above, this interaction will determine the periodicity
of the lamellar stack.

Further reading
Again the best references are Safran’s Statistical Thermodynamic of Interfaces (Chapter 6) and
the proceedings of the Les Houches summer school, Liquids at Interfaces (see chapter 7).
In the latter see in particular the lectures by W. Helfrich and by J. Meunier.
P.M. Chaikin and T.C. Lubensky, Principles of Condensed Matter Physics, Cambridge
University Press, Cambridge, 1995, has a long discussion of membranes and generally
speaking of fluctuating interfaces.
The book edited by R. Lipowsky and E. Sackmann, Structure and Dynamics of Membranes,
volume 1, Handbook of Biological Physics, Elsevier, Amsterdam, 1995, contains many
interesting and recent experimental contributions.

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