This action might not be possible to undo. Are you sure you want to continue?

BooksAudiobooksComicsSheet Music### Categories

### Categories

### Categories

Editors' Picks Books

Hand-picked favorites from

our editors

our editors

Editors' Picks Audiobooks

Hand-picked favorites from

our editors

our editors

Editors' Picks Comics

Hand-picked favorites from

our editors

our editors

Editors' Picks Sheet Music

Hand-picked favorites from

our editors

our editors

Top Books

What's trending, bestsellers,

award-winners & more

award-winners & more

Top Audiobooks

What's trending, bestsellers,

award-winners & more

award-winners & more

Top Comics

What's trending, bestsellers,

award-winners & more

award-winners & more

Top Sheet Music

What's trending, bestsellers,

award-winners & more

award-winners & more

Welcome to Scribd! Start your free trial and access books, documents and more.Find out more

Vincent Chu∗ Sebastian Doniach†‡ , April 29, 2005

Abstract In a 1997 paper, Borukhov et al. derived a modiﬁcation to the PoissonBoltzmann equation (PBE) that incorporated steric repulsion due to ﬁnite ion sizes in the case of a solution with ion and counterion species of equal atomic volume.[1] In many systems of interest, the behavior if ions and counterions in solution is essential in understanding a variety of physical and biological phenomena. However, in these systems, the ion and counterion species typically have diﬀerent sizes and so a further modiﬁcation of the PBE must be completed. This write-up will present a derivation of the PBE to a general case with an ion and counterion species of diﬀerent sizes and charges.

1

Background

This paper describes a generalization of the Poisson-Boltzmann equation (PBE) ﬁrst published by Borukhov.[1] In his paper, Borukhov modiﬁed the PBE to take into account the ﬁnite size of two equal-volume ion species in solution. This paper builds upon that work by relaxing the requirement that both ion species be composed of ions of equal size. The modiﬁed PBE was obtained through a variational method by minimizing the free energy of a lattice gas with respect to the the ion concentrations and the electric potential ψ. Borukhov’s modiﬁcation to the PBE for an ion solution composed of a positive ionic species with charge +e and negative ion species of −ze is:

2

ψ=

4πzec− b

ezβeψ − e−βeψ 1 − φ0 + φ0 (ezβeψ + ze−βeψ )/(z + 1)

(1)

where φ0 = (z + 1)a3 c− , a3 is the volume of a single ion (assumed b to be the same for both positive and negative ions), and c− is the bulk b

of Applied Physics, Stanford University of Physics, Stanford University ‡ Correspondence should be sent to: McCullough Building, 476 Lomita Mall, Stanford, CA 94305-4045. Email: doniach@drizzle.stanford.edu

† Department ∗ Department

1

concentration of negative ions. Note that the original PBE is recovered in the limit of very small ion concentrations (φ0 → 0):

2

ψ=

4ψzec− h b

ezβeψ − e−βeψ

i

(2)

In many physical and biological systems of interest where the interaction of ionic solutions is an important consideration, the PBE equation has long been employed to model the behavior of the ions in solution, particularly around charged objects like proteins. However, the PBE equation is of limited use in these situation because it neglects the ion size as noted before. Borukhov’s solution is a step forward but suﬀers from the fact that in most ion solutions, the two ionic species are typically not of equal size.

2

Bulk Ionic Solutions as Lattice Gases

Consider a ionic solution composed of two species: a positive ion species carrying charge +e and a negatively charged counterion species of charge −ze. Let the volume of the negatively charged ions be a3 and the volume of the positively charged ions ka3 .1 We also impose a charge neutrality condition:

+ − Nb = zNb ± Nb

(3)

where give the total number of positive/negative ions in the bulk solution. We wish to model this system as a cubical lattice gas with a lattice spacing a3 . In our model, the size of the largest ion sets the scale of the lattice. For a lattice gas with N total sites, the volume of the gas is simply V = N a3 . For the lattice gas as a whole, the partition function is given by:

("

Z=

k X n

#

)N

n=0

k

x

n

+y

= (1 + x)k + y

h

iN

(4)

where x ≡ eβµ+ , y ≡ eβµ− and µ± is the chemical potential of the positive and negative ion species. Note that the local potential ψ does not enter into the partition function because the solution as a whole is neutral. The equilibrium number of each ion species is simply given by: 1 ∂[log Z] kx(1 + x)k−1 =N β ∂µ+ (1 + x)k + y y 1 ∂[log Z] =N β ∂µ− (1 + x)k + y

+ Nb − Nb

= =

(5)

**We can deﬁne the following bulk concentrations n± and c± : b b
**

1 In general, positively charged ions tend to have smaller radii than negatively charged ions; hence we choose the smaller ion species to be the positively charged one.

2

c + a3 b c − a3 b

≡ ≡

n+ ≡ b n− ≡ b

+ Nb kx(1 + x)k−1 = N (1 + x)k + y − Nb y = N (1 + x)k + y

(6)

c± gives the bulk number density per volume while n± gives the bulk b b number density per lattice site of the positive and negative ion species. Note that the charge neutrality condition implies that:

+ Nb − Nb

=

n+ b =z n− b

(7)

We would like to obtain a relationship between the chemical potentials µ± and the bulk concentrations of ions. Eqs. 6 deﬁne this relationship; solving these equations for x and y yields: (n+ /k) b 1 − n− − n+ /k b b (zn− /k) b 1 − (k + z)n− /k b n− b 1 − n− b n− b 1 − n− b

x ≡ eβµ+

= =

y ≡ eβµ−

= =

1 − n− b 1 − n− − n+ /k b b

k k

1 − n− b 1 − (k + z)n− /k b

(8)

where we have used the charge neutrality condition to eliminate n+ b (Eq. 7). Eqs. 8 sets the relationship between the chemical potentials µ± and the bulk concentration of ions, an externally controlled parameter.

3

Statistics at Individual Lattice Sites

We now examine the concentrations of ions at individual lattice sites; for single lattice sites, the charge neutrality condition (Eq. 7) no longer applies and now the eﬀect of the electric potential ψ must be taken into account, treated in the context of this theory as a mean-ﬁeld. Howver, the partition function for each individual site is very similar to the partition function of the bulk solution (Eq. 4) and we may make immediate use of the results in the prior section. The partition function of a single lattice site is: Z = (1 + x)k + y (9)

where we now deﬁne x ≡ eβ(µ+ −eψ) and y ≡ eβ(µ− +zeψ) . We can then immediately write down the relations between the concentrations at individual lattice points and the Boltzmann factors x, y:

3

c + a3 c − a3

≡ ≡

n+ ≡ n− ≡

N+ kx(1 + x)k−1 = N (1 + x)k + y N− y = N (1 + x)k + y

(10)

We can now then express the Boltzmann factors x, y as functions of the concentrations in the same way as the previous section (Eqs. 8). (n+ /k) 1 − n− − n+ /k n− 1 − n−

x ≡ eβ(µ+ −eψ) y ≡ eβ(µ− +zeψ)

= =

1 − n− 1 − n− − n+ /k

k

(11)

Note that in this case, the concentrations are spatially varying functions of position from lattice site to lattice site. The free energy is simply F = −τ log Z where τ = 1/β. The entropy can then be determined by taking the derivative with respect to τ : S = −n+ log (n+ /k) − n− log (n− ) − k(1 − n− − n+ /k) log (1 − n− − n+ /k) +(1 − n− ) log (1 − n− )k−1 (12)

**4 Modiﬁcation of the Poisson-Boltzmann Equation
**

Poisson’s equations allows us to solve for the electric potential ψ given a particular charge distribution ρ:

2

ψ=−

4π

ρ

(13)

where is the dielectric constant of the solvent medium. For our lattice gas the net charge density at each lattice site is simply: ρ = (en+ − zen− )/a3 = ec+ − zec− (14)

Eq. 13 and Eq. 14 can be combined to yield the modiﬁed PoissonBoltzman Equation: 4πe (zn− − n+ ) (15) a3 Substituting Eqs. 10 for the concentrations n± and Eqs. 8 for eβµ± yields the ﬁnal modiﬁed Poisson-Boltzmann equation:

2

ψ=

2

ψ=

**4πzec− (1 − c− a3 )k−1 eβzeψ − e−βeψ 1 − c− a3 − z(1 − e−βeψ )c− a3 /k b b b b 1 − c− a3 − z(1 − e−βeψ )c− a3 /k b b
**

k

k−1

+ c− a3 (1 − c− a3 )k−1 eβzeψ b b (16)

4

If we deﬁne the constant φ0 ≡ (k + z)c− a3 /k to be the bulk fraction b of a lattice cell volume occupied by ions, we can re-write the PoissonBoltzmann equation in the following form:

− 4πzec− (1 − c− a3 )k−1 eβzeψ − e−βeψ 1 − φ0 + (zcb a3 /k)e−βeψ b b k−1

2

ψ=

1 − φ0 + (zc− a3 /k)e−βeψ b

k

+ c− a3 (1 − c− a3 )k−1 eβzeψ b b (17)

**5 Obtaining the PBE Through Variational Methods
**

It should be mentioned that the modiﬁed PBE (Eq. 17) can be obtained through a variational principle by writing down the free energy F − T S of the lattice gas and minimizing it with respect to the electric potential ψ and the ion concentrations. For a lattice gas, the total free energy is obtained by intergrating the free energy density over all lattice sites:

Z h

U −T S

= =

−

kb T a3

Z

8π

**| ψ|2 + ec+ ψ − zec− ψ − µ+ c+ − µ− c− dV c+ a3 log (c+ a3 /k) + c− a3 log (c− a3 )
**

i

i

+k(1 − c− a3 − c+ a3 /k) log (1 − c− a3 − c+ a3 /k) − (1 − c− a3 ) log (1 − c− a3 )k−1 dV (18)

Minimizing Eq. 18 with respect to the potential ψ yields Poisson’s equation (Eq. 15). Variation with respect to c± yields the relations Eqs. 10; together these three sets of equations yields the modiﬁed PBE (Eq. 17).

References

[1] I. Borukhov, D. Andelman, and H. Orland, Physical Review Letters 79 (3), 435-438 (1997).

5

2007 ExamMT328-sh6-13.14aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaMT328-sh6-13.14aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaMT328-sh6-13.14aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaMT328-sh6-13.14aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaMT328-sh6-13.14aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaMT328-sh6-13.14aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaMT328-sh6-13.14aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaMT328-sh6-13.14aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa

by Phyo Thiha

Are you sure?

This action might not be possible to undo. Are you sure you want to continue?

We've moved you to where you read on your other device.

Get the full title to continue

Get the full title to continue listening from where you left off, or restart the preview.

scribd