Non-equilibrium thermodynamic approach

Part I
Jean-eric.wegrowe@polytechnique.edu

• 1) Short introduction to equilibrium thermodynamics

• 2) Examples of simples transport equations

• 3) Cross-effect example 1: The thermoelectric effect

• 4) Continuity equations = conservation laws

• 5) Derivation of the transport equations

• 6) Onsager reciprocity relations

• 7) Drift-diffusion-reaction processes

• 8) Cross-effect example 2: The Hall effect 31 Slides

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 Non-equilibrium thermodynamics:
Application of the first law
a) Definition of the system by a set of extensive variables and corresponding densities:

Entropy
Statistical ensemble: The density n(r) is equivalent to
Numbers of particles Energy
the probability distribution of the particles.

b) Conservation laws c) First law (Energy) : E(s, ni) = state function

conjugate
variables
Irreversibility = Local equilibrium assumed
internal production of entropy

Fluid mechanics Inertia: not under consideration

here (Kinetic theory only)

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 Non-equilibrium thermodynamics:
application of the second law
Conservation laws: (1) First law (energy density e = E/v) Internal power only
(adiabatically closed system)

(2) -div(JE) Eq.(2)

(3) (4)
Entropy production:
Inserting Eq.(1) and
Eq. (2) in Eq.(4)

we use the formula of the divergence

of the product of a scalar by a vector
Definion of the
Identification with Eq.(3) Entropy flux heat current
(from the entropy current)

Each force defines

a « local equilibrium » sum of the products of generalized forces by the corresponding flux
« Internal entropy production »
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Internal entropy production:
2d law (adiabatic closed system)
Transport equations
Definition of the transport
coefficients in terms of
Onsager Matrix
Justification of the Onsager matrix for thermoelectricity used in slide 15 of LECTURE VII:
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Transport equations
Second law of thermodynamics:
Sufficient condition: I is a
positive definite quadratic form
Flux in the space
of internal degrees
Curie principle: no coupling
of freedom between scalars and vectors (and tensors).
A : chemical affinity force conjugate to y:
Electric force due to an
electic generator
(reservoir of charges)
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 Reaction-diffusion equation

Continuity Eq. Transport Eqs. and

Inserting Eq.(2) in Eq.(1) (T=cst)

mi(ni) = Implicit equation

CASE OF INDEPENDENT BROWNIAN PARTICLES IN A POTENTIAL.

Needs the knowlege of the functions m(n): n0 is the density at equilibrium and mi0 describes the properties of particles i
Density of particle in
the configuration space
Density n at local equilibrium = Boltzmann distribution = probability density distribution

Like the equations for probability distribution n i => stochastic equation!

Without reaction Aj = 0 : drift-diffusion equation (Lecture VI)

- One dimension x (D and L cst) Random walk in an « environment »
Einstein Relation:
+ deterministic force = Drift

Diffusion Drift now h = L/n Drift Diffusion

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 Non-equilibrium thermodynamic approach
Jean-eric.wegrowe@polytechnique.edu

• 1) Short introduction to equilibrium thermodynamics

• 2) Examples of simples transport equations

• 3) Cross-effect example 1: The thermoelectric effect

• 4) Continuity equations = conservation laws

• 5) Derivation of the transport equations

• 6) Onsager reciprocity relations

• 7) Drift-diffusion-reaction processes

• 8) Cross-effect example 2: The Hall effect

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 Onsager reciprocity relations

Nobel Award Ceremony: 1968

Lars Onsager
1903 - 1976

Prof. Claesson – Royal Swedish Academy of Sciences

«Universal natural law » => fundamental symmetry = Time reversal
Transport coefficients
invariance of the microscopic processes.
(Onsager matrix)
No dissipation at the microscopic scale.

Non-equilibrium thermodynamics flux-force relation :

Transport cross-coefficients i≠j such that: time inversion symmetry

/ axial vector reversal
or (U(1) Gauge symmetry)

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 Three kinds of forces: (1) dissipative (damping),
(2) conservative (derived from potential)
(3) non-conservative non-dissipative (change of reference frame)

Lorentz Force:

Consevrative force
Rotating frame (w cst):
CORIOLIS force: G.-G. de Coriolis,
1792 – 1843
Ecole Polytechnique

Effective magnetic field:

2m/q : inverse of the gyromagnetic ratio 1/g

Onsager reciprocity relation « of the second kind »

Geometrical phase
Gauge invariance Gauge invariance, anholonomy, Berry phase, Hannay angle, ...

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 Non-equilibrium thermodynamic approach
Jean-eric.wegrowe@polytechnique.edu

• 1) Short introduction to equilibrium thermodynamics

• 2) Examples of simples transport equations

• 3) Cross-effect example 1: The thermoelectric effect

• 4) Continuity equations = conservation laws

• 5) Derivation of the transport equations

• 6) Onsager reciprocity relations

• 7) Drift-diffusion-reaction processes

• 8) Cross-effect example 2: The Hall effect

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 Cross-effect: example 2
Hall effect (without screening)
Ohm’s law: Onsager reciprocity relation II
Time-inversion symmetry 
at micro scale Lorentz force:
if rotation of p
B

Isotropic otherwhise

False : the Hall field ey does not generate the current Jx (for ex =0)! It is a consequence not a cause.

We have to take into account the constraints imposed to the system!

Matrix inversion = galvanostatic:
The «current» generates the « force»
(like for the Coriolis force).

The courant Jx generates the Hall field ey

and Jy=0 (at stationary states)
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 Hall effect including screening
Chemical potential
n(y) : density of
n0 : electro-neutrality
electric charges

V(x,y) Electric potential

Jx0
In degenerate metal (Fermi temperature)

in non-degenerate semiconductor Mobility dn > 0

constant
Ohm’s law: Conductivity: Poisson law
dn(y)= n(y) – n0 => electric field along y

Onsager
reciprocity Maxwell-Gauss
relations

Simeon Denis Poisson Imposed induced

1781-1840. X 1798
Drift-diffusion equation for the Hall effect: Professor at Polytechnique

Drift Diffusion Drift Diffusion

Two diffusion coefficients :
(Einstein’s relation)
Well-known equation (validation of the thermokinetic approach)
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