The Clausius-Mossotti Equation

Ottaviano Mossotti (1850) and Rudolf Clausius (1879)

Jason Rich

McKinley Group Summer Reading Club

“Familiar Results and Famous Papers”
August 17, 2007
Jason Rich, McKinley Group Summer Reading Club, 8/17/07

Ottaviano Fabrizio Mossotti (1791-1863)

• Italian physicist and mathematician
– Completed studies at University of Pavia
in 1811 at age 20

• Contributions in:
– Astrophysics (Brera Observatory, 1813 – 1823)
– Molecular physics

• Interesting facts:
– Part of a secret society against the occupying Austrian government
– Escaped to London in 1823, then to Buenos Aires, Argentina, until 1835
– Returned to Italy in 1840, where he taught until his death

http://liberti.dhs.org/liberti/maths-history/mossotti/mossotti.html 2
Jason Rich, McKinley Group Summer Reading Club, 8/17/07

Rudolf Julius Emmanuel Clausius (1822-1888)

• German thermodynamicist extraordinaire
– Doctoral thesis on atmospheric optics from
University of Halle in 1847
– Taught in Berlin, Würzburg, Bonn, and briefly at
ETH Zürich

• A “founding father” of thermodynamics

– Revised the first and second laws of thermo
– Mathematically described entropy and coined the
term

Clausius-Clapeyron Equation
Famous quotes:
“The energy of the universe is constant” ⎡ d ln ( P ) ⎤ ΔH vap
⎢ ⎥ =−
“The entropy of the universe tends to a maximum” ⎣ d (1 T ) ⎦[ L −V ] R

http://en.wikipedia.org/wiki/Rudolf_Clausius 3
Tester, J.W., Modell, M. (1997), Thermodynamics and Its Applications, 3rd Ed., Prentice Hall, New Jersey, p. 681.
Jason Rich, McKinley Group Summer Reading Club, 8/17/07

The Equation
ε = bulk dielectric constant
ε −1 χ Nα ⎛ A 2 ⋅ s4 ⎞
ε 0 = dielectric permittivity of free space ⎜ 3
= = m ⋅ kg
⎟
ε + 2 χ + 3 3ε 0 χ = bulk dielectric susceptibility ⎝ ⎠
⎛ A 2 ⋅ s4 ⎞
α = molecular polarizability ⎜ ⎟
ε −1 χ 4 ⎝ kg ⎠
= = π N αV αV = molecular polarizability volume ( m3 )
ε +2 χ +3 3 N = Number of dipolar molecules per unit volume

• Relates bulk, macroscopic quantity (ε or χ) to molecular quantity (α)

• Derived independently (supposedly) by Mossotti (1850) and Clausius

(1879)
Clausius, R. (1879), Die Mechanische Wärmetheorie, 2, Braunschweig, p. 62 – 97.
Mossotti, O.F. Mem. Di Math, e Fisica d. Soc. Italiana d. Scienze, 24, 2, (1850), 49. 4
Jason Rich, McKinley Group Summer Reading Club, 8/17/07

What’s the big deal?

• Useful
– Clarifies molecular origin of dielectric constant ε −1 χ Nα
– Allows calculation of molecular polarizability = =
from measurements of ε
ε + 2 χ + 3 3ε 0

• Derivation is tricky, yet applicable to many physical situations:

– What is the local electric field of a dielectric on a molecular scale?

Eloc Eext
Eext
p
Eloc = ?
5
Jason Rich, McKinley Group Summer Reading Club, 8/17/07

Derivation Path
Eext
polarizes Relate Eext Plug Eloc into eqn:
to Eloc Solve for χ
dielectric P = ∑ N i pi =N ε 0α Eloc = ε 0 χ E
i

Relatively long
range interactions Eloc

between dipoles
(U ~ 1/r3)
Key Assumptions:
a) Only dipolar interactions

Split material b) All dipole moments are identical

into discrete c) Molecules distributed isotropically
and continuum
regions d) Fluctuations negligible
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Jason Rich, McKinley Group Summer Reading Club, 8/17/07

Clarification and Correction of Eqn 13.2

Electric field from a polarized body: M
p ir P (ξ ,η , ζ ) dV = ∑ p n
φn ( x, y, z ) = n n3 pn = dipole moment of molecule n
4πε 0 rn n =1

P (ξ ,η , ζ )ir ∇ 2 iP ( R 2 ) 3
dφ =
Pir
dV → φ=∫ d ξ dη d ζ E ( R ) = ∇1 ∫ d R2
4πε 0 r 3
4πε 0 r 3 body
4πε 0 R12
V

Define two different gradient ∂ ∂ ∂ ∂ ∂ ∂

∇ F = ex + e y + ez ∇S = ex + ey + ez
operators for the two coordinates: ∂x ∂y ∂z ∂ξ ∂η ∂ζ
⎛1⎞ r 1 ⎡ ⎛ 1 ⎞⎤
φ ( x, y , z ) =
4πε 0 V∫ ⎢⎣ ⎝ r ⎠ ⎥⎦
We now recognize: ∇ S ⎜ ⎟ = 3 Pi ∇ S ⎜ ⎟ dV
⎝r⎠ r
⎛ P ⎞ ∇ iP ⎡ ⎛ 1 ⎞⎤
The dot product is expanded: ∇ S i⎜ ⎟ = S + Pi ⎢∇ S ⎜ ⎟ ⎥
⎝r⎠ r ⎣ ⎝ r ⎠⎦
pn rn = ( x − ξ ) e x + ( y − η ) e y + ( z − ζ ) e z
Then use the divergence theorem to get:
(ξ,η,ζ)
dielectric (x,y,z) P i dS ( −∇ S iP ) dV
z y
φ ( x , y , z ) = ∫S 4πε 0 r V∫ 4πε 0 r
+

r ⎡ P i dS
E ( x, y, z ) = −∇ F ⎢ ∫ +∫
( −∇ S iP ) dV ⎤
⎥ 7
x ⎣S 4πε 0 r V
4πε 0 r ⎦
Jason Rich, McKinley Group Summer Reading Club, 8/17/07

Finding the Local Field, Eloc

• Adopted from Frölich, Theory of Dielectrics, 1958.
• Consider a macroscopic dielectric in an external field
e+ e-

a0 E
Eext E

• Consider a cubic lattice of dipoles

• Assumptions:
– Charge separation << a0
– Properties in sphere are same as bulk, fluctuations negligible
– Only dipolar interactions
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 Jason Rich, McKinley Group Summer Reading Club, 8/17/07

Finding the Local Field, Eloc

• Assume that applying E polarizes each lattice site the same amount:
Restoring force ~ r balances the force from Eloc
e- 2
⎛ e ⎞
E Eloc e+ Restoring force = c 2 r = eEloc → p = e r = ⎜ ⎟ Eloc
r ⎝c⎠
Separate contributions of Eloc into inside and outside of sphere: Eloc = Ein + Eout
Find Ein by summing each dipole interaction in the sphere:
p2
(
Interaction energy between 2 identical point dipoles = U ij = 3 1 − 3cos 2 (θij )
lij
)
lij = Distance between dipoles i and j
Since dipoles are in lattice, lij = (ma0, na0, qa0) where m, n, q are integers
p2 m 2 + n 2 − 2q 2
U = ∑ U ij = 3 ∑ =0
a0 m ,n ,q ( m + n + q )
2 2 2 52

e+ e-

So Ein = 0 !
a0
E
Eext 9
Jason Rich, McKinley Group Summer Reading Club, 8/17/07

Finding the Local Field, Eloc

Eloc = Ein + Eout
Calculate Eout macroscopically Eout = E – Es

Es = “self-field” = field at center of a

permanently polarized sphere
Es P
Eext E
- Can be found with a standard calculation
4π
ES = − P
So finally: 3
4π
Eloc = Ein + Eout = E − ES = E + P Here the macroscopic ε −1
3 P= E
ε +2 relation between P and E is: 4π
Eloc = E “Lorentz formula” 2
3 And the microscopic 1 ⎛e⎞
p = P = ⎜ ⎟ Eloc
Plug into Eloc the relation is: N ⎝c⎠
microscopic equation
⎛e⎞ ε +2 ε −1
2
ε − 1 4π ⎛ e ⎞ 4
2
P= N⎜ ⎟ E= E = N ⎜ ⎟ = π N αV
⎝c⎠ 3 4π ε +2 3 ⎝c⎠ 3 10
Jason Rich, McKinley Group Summer Reading Club, 8/17/07

Limitations of the Equation

• Condensed systems (high density)
– van der Waals and multipole forces can become significant
– If we rearrange the C-M eqn, we get:

3 + 8π NαV Critical density at N =

3
ε= 4παV
3 − 4π NαV
Not observed in
experiments

• Systems of permanently polar molecules

– The derivation assumes that all polarity is induced
– Permanent dipoles require a correction to the local field, as will be seen
Böttcher, C. J. F. (1952), Theory of Electric Polarisation, Elsevier Publishing Co., New York, p. 199 - 212 11
Jason Rich, McKinley Group Summer Reading Club, 8/17/07

Onsager’s Correction to Local Field

• When calculating Eloc, we neglected the coupling of the center
dipole with the surrounding ones
e+ e-

a0
E
Eext

• Onsager corrected this: Ecorr = Eloc - Ereaction

2χ p
Ereaction =
3 + 2 χ 4πε 0 a 3
e+ e-
⎛ 2 ⎞ Goes to C-M eqn
This yields: χ ⎜1 + χ ⎟
a ⎝3 ⎠ in low density limit
Nα =
1+ χ
3⎛ 2 ⎞
χ = ⎜⎜ Nα − 1 + 1 + N + N α ⎟⎟
2 2
12
4⎝ 3 ⎠
Jason Rich, McKinley Group Summer Reading Club, 8/17/07

Alternative Derivations Abound

• Hannay gives a derivation which involves no splitting into
inner and outer parts
– Uses the full expression for field of a dipole:

3 ( pir ) r p 4π
E= 5
− 3− pδ ( r )
r r 3

– Local field correction results naturally

• Other derivations based on quantum mechanics
– Attempt to account for non-localization of electrons at lattice
points and other more complex phenomena
– Eg, Adler, Onodera
S. L. Adler, Phys. Rev. 126 (1962) 413.
J.H. Hannay Eur. J. Phys. 4 (1983) 141. 13
Y. Onodera, Prog. Theo. Phys., 49 (1973) 37.
Jason Rich, McKinley Group Summer Reading Club, 8/17/07

Applications in Other Areas

• Dispersion properties in optical fibers
– (P. Melman and R. W. Davies J. Lightwave Tech. 3 (1985) 1123.

• Relating molar refractivity to bulk refractive index

– (Boling, Glass, Owyoung, IEEE J. Quant. Electronics 14 (1978)
601.)

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Jason Rich, McKinley Group Summer Reading Club, 8/17/07

Thank you for your attention!

ε −1 χ 4 ε −1 χ Nα
= = π N αV = =
ε +2 χ +3 3 ε + 2 χ + 3 3ε 0

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