Poisson-Boltzmann theory, Oct 22, 2013 1

1 Introduction
Electrostatic interactions are found to be relevant for virtually all biomolecular systems
and processes. Understanding the underlying physics in these processes makes huge
impact on life science, and the Poisson-Boltzmann equation constitutes one of the most
fundamental approaches to treat electrostatic eects in solution. It is a partial dierential
equation that describes the electrostatic interactions between charged molecules and the
mobile ions in the ionic solutions. It solves for the electrostatic potential distribution, and
its formulation can be derived from the Poisson equation and Boltzmann distribution.
The equation is particularly important in the elds of molecular dynamics (MD) and
biophysics because:
a. It is widely used in modeling implicit solvation, an approximation of the eects of
solvent on the structure and interactions of proteins, DNA, RNA, and other molecules
in solutions of dierent ionic strength. This technique saves signicant amount of time
in the MD calculations.
b. It unveils the electrostatic forces between biological components and helps describing
the swelling properties of the biological tissues. For example, the theory can be used to
describe the restoring force mechanism between the collagen brils in the human cornea,
and thus explain the underlying control mechanism of the bril lattice that maintains
the corneal transparency.
2 Poisson-Boltzmann theory
2.1 Poisson equation
Consider a piece of polyelectrolyte gel immersed in a bath solution (Fig.1). Due to the
presence of (negative) xed charges within the gel, the mobile ions are redistributed and
there exists an electrostatic potential dierence between the gel and the bath. Within a
representative unit cell of the polyelectrolyte gel, the electrostatic potential is governed
by the Poisson equation
(
w
(x)(x)) = (x) (2.1)
where
w
is the dielectric permittivity of the solution. (x) is the local charge density
and is expressed as the sum of the contribution from two sources: the xed charges and
the mobile ions.
(x) =
x
(x) +
M

i=1
Fz
i
C
i
(x) (2.2)
where
x
(x) is the xed charge distribution and C
i
(x) is the i
th
ion species concentration
and z
i
the associated valence. F is the Faraday constant.
Poisson-Boltzmann theory, Oct 22, 2013 2
Figure 1: An electrolyte gel immersed in a bath solution.
2.2 Boltzmann distribution of the mobile ions
The mobile ion distribution C
i
(x) can be derived as follows. In the transient state, the
molar ux of species i can be expressed in the form of Nernst-Planck equation:
j
i
= vC
i
z
i
D
i

F
RT

C
i
D
i
C
i
(2.3)
vC
i
Flow due to convection
z
i
D
i

F
RT

C
i
Flow due to electro-osmosis
D
i
C
i
Flow due to diusion
where v is the velocity of convective ow and D
i
the diusion coecient of species i. At
equilibrium state where the Poisson-Boltzmann theory is concerned, j
i
= v = 0 and thus
we have:

z
i
F
RT
=
C
i
C
i
(2.4)
and thus
C
i
= C

i
exp

z
i
F
RT

(2.5)
where C

i
is the concentration of the species i in the bath solution (where the electrostatic
potential = 0).
Poisson-Boltzmann theory, Oct 22, 2013 3
2.3 The Poisson-Boltzmann equation
The PB equation can be obtained by combining eq.(2.1-2.2) and eq.(2.5):
(
w
(x)(x)) =
x
(x) +
M

i=1
Fz
i
C

i
exp

z
i
F
RT
(x)

, x
electrolyte
(2.6)
Where
electrolyte
refers to the electrolyte domain. Assuming a constant dielectric permit-
tivity and a binary electrolyte (e.g. NaCl) with concentration C

+
= C

= C
0
, eq.(2.6)
can be simplied as:

2
(x) =

x
(x)

2FC
0

w
sinh

F(x)
RT

, x
electrolyte
(2.7)
If the xed charges are rather surface charges, then the following boundary should be
enforced:
(x) n =

x

w
, x
electrolyte
(2.8)
where
x
is the charge density on the surface denoted by
electrolyte
.
2.4 Electrostatic free energy
The mean-eld approximation of the free energy for a binary electrolyte can be expressed
as a functional of , which is stationary at the solution of the PB equation in the form:
F
el
=

electrolyte

x
(x)(x) 2RTC
0

cosh

F(x)
RT

w
2
|(x)|
2

d (2.9)
The rst and second terms in eq.(2.9) measure the electrostatic energy of the xed charges
and ionic charges respectively, and the last term measures the contribution from the
electric eld.
2.5 The Debye length
The Debye length is the characteristic distance in an electrolyte over which the potential
of a charged surface decays by 1/e. For the physiological condition where C
0
150mM,
this is estimated as:

1
=

w
RT
2F
2
C
0
0.78nm (2.10)
In the PB theory, the Debye length is an important measure of the shielding eect created
by the mobile ions. The higher bath concentration, the stronger shielding eect from the
ions and thus the lower Debye length the electrolyte has (the electrostatic potential drops
rapidly from the charged surface in such case).