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On Debye-Hückel's Theory

Article in EPL (Europhysics Letters) · August 1993

DOI: 10.1209/0295-5075/24/8/012

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EUROPHYSICS LETTERS 10 December 1993
Europhys. Lett., 24 (S), pp. 693-698 (1993)

On Debye-Huckel’s Theory.
I. M. MLADENOV
Central Laboratory of Biophysics, Bulgarian Academy of Sciences
Acad. G. Bonchev Str., B1. 21, 1113 Sofia, Bulgaria

(received 15 March 1993; accepted in final form 22 October 1993)

PACS. 82.45 - Electrochemistry and electrophoresis.

PACS. 02.20 - Group theory.

Abstract. - A one-parameter deformation family of Debye-Hiickel’s model, sharing the

appropriately modified rotational symmetry of the classical theory, is introduced and solved in a
closed form. It is shown that, when the deformation parameter is set equal to zero, one regains
Debye-Hiickel’s model and results.

When one studies a many-particle system in which the interaction between the
constituents is strong enough, the most simple way to account for this interaction is to use
the notion of mean or molecular field. This approach has been used by Debye and Huckel [ll
in order to find the electrostatic component of the free energy which turns out to be
equivalent t o the work done for charging a sphere (macroion) in a solution. This electrostatic
component can be expressed as an integral

we1 = j+dq

taken over all charged parts from q = 0 to its final value. It is evident that the problem with
finding We, goes through the fundamental problem of classical electrostatics where one tries
to determine the (electrostatic) potential (field) at every point in a space for a given
distribution of charges. In many of such situations the ambient space is modelled as a
homogeneous medium in which the potential at a distance r from a point charge Q is given by
Coulomb’s law
+ = &/ET, (2)
where E is the dielectric constant, a quantity that indicates the extent to which the
electrostatic effect of the charge is screened by the medium. In the most general form the
problem covers cases where the dielectric constant can vary in space. In the regions of
uniform dielectric constant without free charges the electrostatic potential +
satisfies
Laplace’s equation at every point r:

A+(r) = 0 , +
A = a2/ax2 a 2 / a y 2 + a 2 / a z 2 . (3)
694 EUROPHYSICS LETTERS

If there are charges present this equation is replaced by Poisson’s equation

where p(r) is the charge density at the point r.

By solving either Laplace’s or Poisson’s equation, wherever appropriate, one gets local
solutions depending on integration constants. The global solution is obtained by matching
different solutions at common boundaries. Using the continuity of $, i.e.

$1 = $2 (5)

and that of its (normal) gradient

arranges the problem with the integration constants and in this way the globalization of $ is
achieved. When the boundary is a charged surface with surface charge density 0, (6) is
replaced by

It should be mentioned that analytical solutions of these equations exist only for some
simple geometries, while more complicated cases are treated by numerical methods. Here we
shall consider the Debye-Huckel model and its modification. This modification includes the
Debye-Huckel model as a special case and, what is also interesting, retains its explicit
solvability.
The classical Debye-Huckel model is shown in fig. 1. It is assumed that the macroion in
whose free electrostatic energy we are interested is a low dielectric spherical medium of
radius R1 (region I) surrounded by a solvent with an external dielectric constant E , and
mobile counterions. In the low dielectric region I and in the ion exclusion region I1 (sphere of
radius R,) we can apply Laplace’s equation, while in the high dielectric region I11 (which is
supposed to be infinite with the same dielectric constant = E , ) we should apply Poisson’s
equation. It is also assumed that the total charge of the central ion q is distributed uniformly
on the boundary between regions I and I1 where its surface charge density is
0 = Q/4?&1.

Fig. 1. - Geometry and regions I, 11, I11 of the Debye-Huckel model.

I. M. MLADENOV: ON DEBYE-HUCKEL'S THEORY 695

Spherical geometry means rotational symmetry which can be expressed by saying that the
generators L~= Eijkxja/axk, i , j , IC = 1 , 2 , 3 of the so@) Lie algebra [ei,
Zjl = E i j k Z k
satisfy
Ei+ = ( E $ d a / a x k ) + = 0 , i , j , IC = 1 , 2 , 3 , (8)
and consequently
2 2 Y = (Z1" +e; +L&b = 0 . (9)
Here we also recall that, written in spherical polar coordinates (r,e, p), the Laplacian
operator looks as follows:
+
A+ = (l/r2)a/3r(r2a+/ar) ( l/r2)SZ$, (10)
where SZ = Z2 is its angular part.
Spherical symmetry means that in the regions I and 11, free of movable charges, the
equation that has to be solved is
A$ =d2+/dr2+ (2/r)(d$/dr) = 0 . (11)
It is easy to see that the latter is equivalent to
d2(r+)/dr2= 0 (12)
whose solution

+ = c + C/r (13)
depends on two arbitrary real constants, C and 6. Now, as the frst region contains the
+
singular point r = 0 (of the solution) and as we are looking for bounded, we are forced to
make the restriction = 0, i.e.
+ = C in region I . (14)
All points in region I1 are regular for a + of the form (13) and that is the reason why + can be
written there as

+ = B + B/r in region 11. ( 15)

The situation with the third region is quite different as now we must solve the
equation
+
A+ = d2+/dr2 (2/r)(d+/dr) = I C $~ , ( 16)
where IC is the so-called Debye-Huckel parameter. This equation has solutions of the
form
+ = A exp [ - K Y ] / Y + A exp [I C T ] / V . (17)
Again, we should pose the second constant A = 0 in order to have only bounded solutions
(this time at infinity r +-CO ), i e .
$ = A exp [ - I C Y ] / ~ in region I11 . (18)
Inserting (14), (15) and (18) into (5)-(7) and solving the obtained linear algebraic equations
696 EUROPHYSICS LETTERS

allows us to specify all integration constants A, B, E, C, and hence $. Explicitly, we

have

It should be noted that these solutions depend only upon E ~ while

, one expects from the
very beginning that they will depend on both dielectric constants. As we shall see, the
presence of the missing constant c 1 will be restored into the solutions of the modified
model.
From the mathematical point of view, the equations with which we will deal further on are
of the so-called Bessel type. This name refers to the second-order linear differential equation
of the form

x2y” + xy’ + (x2 - v 2 ) y = 0 * (22)

Here v can be an arbitrary complex number and, if it is an integer one, then the
function
m
J,(x)= 2 (-
k=O
l)k/k!(v + k)!(X/B)Y+2k (23)

+
is a solution of this equation. When v is not integer, in eq. (23) ( v k)! should be replaced by
r(v + k + l ) , where r is the gamma-function (see, e.g., [ 2 ] ) .In this case a basis of solutions of
(22) is given by J,(x) and J - , ( x ) (defined by the same formula). Actually, closer to our
situation is the equation

x2y” + xy‘ - ($2 + v2)y = 0 , (24)

which is known as the modified Bessel equation and whose space of solutions is spanned by
the modified Bessel functions of the frst kind (when v 2‘)

I,($) = exp[- v x i / 2 1 J v ) i x ) and I-,(x). (25)

Whether v is an integer or not, this equation has another basis of solutions provided by
I,(%) and K,(x). Here
K, (x)= x [ I - , (x)- I , ( x ) ] / 2sin v x (26)
denotes the modified Bessel function of the second kind. It can be shown that K,(x)is a
continuous function of its index v which, in particular, means that

lim K, (x)= K, (x), when v + n E 2 . (27)

Moreover, I , (x)and K, (x)are linearly independent. For real and positive values of v and x
these functions are real. Finally, the equation
I. M. MLADENOV: ON DEBYE-HUCKEL’S THEORY 697

has a basis of solutions given by

I,,(kx) and K,,(kx), (29)
in terms of which we shall express our results.
Now, we move to explain the modification of Debye-Huckel’s theory mentioned before.
We will provide this by a revision of the spherical symmetry of the underlying model. In
analytical form this symmetry has been expressed as the properties of the momentum
operators (see (8) and (9)). On the other hand, these operators are connected with the Poisson
brackets among canonical coordinates in phase space. If we change the canonical symplectic
structure on the classical phase space P = T * ( R 3/{ O}), w = d( z p i dxi) = 2 dpi A dxi
(i = 1,2,3) by adding to w a <<magneticterm,) 0, = - (p/2r3)2 EijkxidxiA dxk,we will have
as a result the deformation of the Poisson brackets among all functions on P. Especially, for
the canonical coordinates on the phase space we will have

The new so@) Lie algebra { M iMj}

, = E,j.ki%fk is generated by
Mi = Li + pxi/r, Li EijkX’Pk i=l,2,3, (31)
and its Casimir operator $i is related t o that of the old i 2
as follows (for more details on this
point see [3]):

M 2 = + g. (32)
+
From now on we assume that the potential is r_tationally @variant with respect to the
modified momentum operators Mi.Substitution of M 2 - ,U’ for L 2 in (10) modifies the radial
part of the Laplacian operator and now the Poisson equation reads
+
r2d2+/dr2 2r(d+/dr) -(IC~@ + p2)+ = 0. (33)
After some analysis, the bounded solution in the third region can be written as

+=M,(~r)/r’/~
v =, ( l +4p2)’/2/2. (34)
The respective bounded solutions in the regions I and I1 are represented by
+ = Cr‘2’ - 1)/2 (35)
and
+ = Br(2v - 1)/2 + Er - ( 2 v + 1)/2
(36)
Placing as before these solutions into ( 9 4 7 ) and solving the so-obtained algebraic
equations we fur the integration constants A , B, E and C. In order to keep their explicit
expressions transparent, the following notations are useful:
x = 1 + EK” - 1 (KR2) + K”+ 1(K&J1& IK” ( K R 2 ) , (37)
+ X€,]R;’/[(2v + 1)€ 2 - XE,],
Y = [(2v - 1)€ 2 (38)
v = ((2, - 1)[€1(R{+ YR;’) - €&{I + (2v + l)€ZYR;’}Ry/2. (39)
698 EUROPHYSICS LETTERS

With the help of the preceding notations we can write the integration constants as
follows:
A = q(R,”+ YR,”)/VK, ( K R ~ ) , (40)
B = a/v, (41)
E = qY/V,
C = q(R{ + YR;’)/VR{ .
Few remarks are in order here. First of all, when we let p + 0, i.e. v + 112 any of these
functions goes smoothly to the value prescribed by the classical Debye-Hiickel’s theory.
Here, we should mention that in [4] and [5] a parameter-dependent permittivity ( r ) has
also been used within the framework of Debye-Huckel theory as a starting point for a more
rigorous treatment via the Poisson-Boltzmann equation [6-91. On the other hand, in [lo] the
authors have shown that beyond some distance the Debye-Huckel solution is the best
approximation to the solution of the Poisson-Boltzmann equation. Now, solutions (34)-(36)
are parameter dependent and this makes them more flexible for satisfying the corresponding
matching conditions. Next, besides ,U,a new free parameter is at our disposal in the solutions
(34)-(36). This is the dielectric constant c2 which can be equated again to E ~ but
, our opinion is
that it must be kept different in order to make the transition from low to high dielectric
regions (c1 < < s3) more realistic from the physical point of view. Finally, the need of
comparing our results to the Tanford-Kirkwood theory [ l l ] is obvious. We hope to report on
this subject elsewhere.
***
This work is partially supported by the Bulgarian National Science Foundation Project no.
K-202192.

REFERENCES

[l] DEBYEP. and HUCKEL E., Phys. Z . , 24 (1923) 185.

[2] WHITTAKER E. and WATSONG., M o d e m Analysis (Cambdrige University Press) 1962.
[3] MLADENOV I., Int. J. Theor. Phys., 28 (1989) 1255.
[4] GOLDSTEIN R. and KOZAKJ., J. Chem. Phys., 62 (1975) 276.
[5] GOLDSTEIN R., HAYP. and KOZAKJ., J . Chem. Phys., 62 (1975) 285.
[6] BURLEYD., HUSTONV. and OUTHWAITE C., Mol. Phys., 27 (1974) 225.
[7] ORTTUNGW., Ann. N.Y. Acad. Sci., 303 (1977) 22.
[81 WARWICKER J. and WATSONH., J. Mol. Biol., 157 (1982) 671.
[9] GILSONM., SHARP K. and HONIGB., J. Comp. Chem., 9 (1987) 327.
[lo] LEBRETM. and ZIMMB., Biopolymers, 23 (1984) 287.
[lll TANFORDC. and KIRKWOOD J., J. Am. Chem. Soc., 79 (1957) 5333.

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