The Boltzmann Equation

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The BBGKY Hierarchy - First Equation

To estimate the relative importance of the different terms in the hierarchy,

we begin by examining the first two equations.
We start with the equation for the single-particle distribution function f1 :
 
q1 − q
Z
∂ ∂U ∂ p⃗1 ∂ ∂V(⃗ ⃗2 ) ∂f2
− · + · f1 = dV2 · ,
∂t ∂⃗q1 ∂⃗ p1 m ∂⃗ q1 ∂⃗q1 ∂⃗
p1

This equation represents the evolution of f1 with contributions from

interactions encoded through f2 .

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The BBGKY Hierarchy - Second Equation

The second equation involves the two-particle distribution function f2 :

  
∂ p⃗1 ∂ p⃗2 ∂ q1 − q
∂V(⃗ ⃗2 ) ∂ ∂
+ · + · − · − f2
∂t m ∂⃗ q1 m ∂⃗ q2 ∂⃗q1 ∂⃗p1 ∂⃗ p2
 
q1 − q q2 − q
Z
3 ∂V(⃗ ⃗3 ) ∂ ∂V(⃗ ⃗3 ) ∂
= d v3 · + · f3
∂⃗q1 ∂⃗
p1 ∂⃗
q2 ∂⃗p2

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Symmetry and Streaming Terms

Note that two of the streaming terms in the previous equation have been
combined using the identity:

q1 − q
∂V(⃗ ⃗2 ) q2 − q
∂V(⃗ ⃗1 )
=−
∂⃗q1 ∂⃗q2
This is valid for a symmetric potential such that:

V(⃗
q1 − q
⃗2 ) = V(⃗
q2 − q
⃗1 )

This combination simplifies the form of the streaming terms.

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Time Scales from Dimensional Analysis

Time scales are estimated via dimensional analysis using typical values:
Typical gas particle speed at room temperature: v ≈ 102 m/s
Macroscopic distance scale: L ≈ 10−3 m
Then, the time scale associated with the external potential U(⃗
q ) is:

L
τU = ≈ 10−5 s
v
This time scale is called extrinsic since it can be lengthened by increasing
system size.

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Collision Duration: An Intrinsic Time Scale

For interatomic interactions described by V, we define the collision

duration time scale:
1 ∂V ∂
∼ ·
τc ∂⃗
q ∂⃗ p
This describes the time two particles spend within each other’s interaction
range:
Short-range interactions: e.g., van der Waals, Lennard-Jones
Typical interaction range: d ≈ 10−10 m
Hence: τc = d
v ≈ 10−12 s
This is typically the shortest time scale in the system.

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Mean Free Time Between Collisions

Additional time scale: mean free time τχ .

This involves collision terms from higher-order equations and gives:
Z Z
1 3 ∂V ∂ fs+1 ∂V ∂ ρs+1
∼ d v · ∼ d 3v ·N
τχ ∂⃗
q ∂⃗ p fs ∂⃗
q ∂⃗p ρs

With particle density n = N

V ≈ 1026 m−3 :

τc 1
τχ ≈ 3
≈ ≈ 10−8 s
nd nvd 2

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Graphical Illustration

Figure: The mean free time is estimated by requiring only one particle in the
volume swept in time τχ .

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Conditions for Boltzmann vs Vlasov Equations

When nd 3 ≪ 1, particle collisions are infrequent: Boltzmann

equation applies.
When nd 3 ≫ 1, collisions dominate: Vlasov equation applies,
collision terms neglected.
The first equation differs by lacking collision terms on the RHS.

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Truncation and Two-Body Dynamics

We truncate the hierarchy after the second equation by setting RHS of the
second to zero.
This implies f2 evolves as an isolated two-particle system:
Streaming terms split into τU−1 and τc−1
First describes center-of-mass motion
Second governs relative motion

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Molecular Chaos

For large separations (much greater than interaction range), particles

behave independently:

f2 (⃗
p1 , q ⃗2 , t) ≈ f1 (⃗
⃗1 , p⃗2 , q ⃗1 , t) · f1 (⃗
p1 , q ⃗2 , t)
p2 , q

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Two-Particle Relaxation and Short-Range Behavior

Out of equilibrium, such as when a barrier is removed and gas expands, f1

evolves over a long time τU , while f2 quickly approaches a factorized form
over the shorter time scale τc .
For |⃗
q2 − q
⃗1 | ≫ d, we use the factorized form:

f2 (⃗
p1 , q ⃗2 , t) ≈ f1 (⃗
⃗1 , p⃗2 , q ⃗1 , t)f1 (⃗
p1 , q ⃗2 , t)
p2 , q

This assumption helps simplify the kinetic theory in the dilute gas limit.

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Behavior at Small Relative Distances

At small relative separations, to determine the collision term precisely, we

analyze how f2 behaves:
  
p⃗1 ∂ p⃗2 ∂ ∂V(⃗q1 − q
⃗2 ) ∂ ∂
· + · − · − f2 = 0
m ∂⃗ q1 m ∂⃗ q2 ∂⃗q1 ∂⃗
p1 ∂⃗ p2

This is the steady-state condition of f2 valid over short scales.

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Center of Mass and Relative Motion Variables

We define center of mass Q ⃗ = (⃗ ⃗2 )/2 and relative coordinate

q1 + q
⃗=q
q ⃗2 − q
⃗1 .
⃗ and rapidly in q
Because f2 varies slowly in Q ⃗ , and similarly in p⃗1 , p⃗2 , we
assume:
∂f2 ∂f2 ∂f2 ∂f2 ∂f2
≫ , ≈− ≈
∂⃗
q ∂Q⃗ ∂⃗
q 2 ∂⃗q 1 ∂⃗q
Then the equation simplifies to:
 
∂V(⃗ q) ∂ ∂ p1 − p⃗2 ) ∂f2
(⃗
· − f2 = − ·
∂⃗
q1 ∂⃗
p1 ∂⃗ p2 m ∂⃗
q

This determines how f2 changes during collisions.

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Collision Integral for f1

The collision term in the equation for f1 becomes:

Z  
df1 3 3 ∂V(⃗ q) ∂ ∂
= d p⃗2 d q ⃗2 · − f2
dt coll ∂⃗q ∂⃗p1 ∂⃗p2
 
p⃗2 − p⃗1
Z
3 3 ∂f2
= d p⃗2 d q ⃗ ·
m ∂⃗
q

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Kinematics of Collision and Scattering

To evaluate the collision integral, we align coordinate a with the direction

of relative momentum p⃗ = p⃗2 − p⃗1 .
We define:
P⃗ = p⃗1 + p⃗2 = p⃗′ + p⃗′ (total momentum)
1 2
p1 − p⃗2 )/2 (relative momentum before)
p⃗ = (⃗
p⃗′ = (⃗
p1′ − p⃗2′ )/2 (relative momentum after)
In an elastic collision, p⃗ rotates by solid angle Ω̂(θ, ϕ).

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Collision Kinematics

Figure: The parameters used to describe the collision of two particles in their
center of mass (at a = 0) frame.

⃗ ′
The Boltzmann ′
Equation 17 / 30
Collision Integral and Relative Motion

The integrand in Eq. (3.35) is a derivative of f2 along relative motion

p⃗ = p⃗2 − p⃗1 .
Z
df1 h i
p1′ , q
= d 3 p2 d 2 ⃗b|⃗v1 − ⃗v2 | f2 (⃗ ⃗1 , p⃗2′ , ⃗b, −, t) − f2 (⃗ ⃗1 , p⃗2 , ⃗b, −, t)
p1 , q
dt coll.

|⃗v1 − ⃗v2 | = |⃗ p1 − p⃗2 |/m

d 2 ⃗b|⃗v1 − ⃗v2 |: flux impinging per unit area d 2 ⃗b
⃗1 .
f2 is evaluated before and after the collision at the same q

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Symmetry and Distribution after Collision

Densities f2 before and after collision must be treated differently.

Streaming implies: f2 (⃗ ⃗1 , p⃗2 , ⃗b, +, t) = f2 (⃗
p1 , q 1 ⃗1 , p⃗′ , ⃗b, −, t)
p′ , q 2
Time reversal allows swapping incoming p⃗1 , p⃗2 with −⃗
p1 , −⃗
p2 .

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Elastic Scattering

Elastic Scattering: A collision process where kinetic energy and

momentum are conserved.
No energy loss to internal degrees of freedom (e.g., no excitation or
deformation).

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 Key Definitions

Scattering Cross Section

dσ
Differential Scattering Cross Section ( dΩ ):

dσ
dΩ
It quantifies the probability of scattering into a solid angle
Total Cross Section (σ):
Z Z 2π Z π
dσ dσ
σ= dΩ = sin ϕ dϕ dθ.
dΩ 0 0 dΩ

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 Key Definitions

Impact Parameter and Scattering Angle

Impact Parameter (b): Perpendicular distance from the scattering
center to the incoming particle’s trajectory.
Scattering Angle (θ): Angle between the incoming and outgoing
trajectories of the particle.

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 Key Definitions

Scattering Geometry

Particles with impact parameter between b and b + db pass through

an annular area:
dσ = 2πb db.
These particles are scattered into a solid angle:

dΩ = sin θ dθ dϕ.

Due to cylindrical symmetry, integrate over ϕ:

dΩ = 2π sin ϕ dϕ.

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 Key Definitions

Relating Impact Parameter to Scattering Angle

Number of particles entering area dσ = 2πb db:

N 2πb db,

where N: incident flux.

the number of particles scatteing in small solid angle dΩ about Ω
direction is given by Ndσ = N(Ω)dΩ

dσ
N = N(Ω)
dΩ
where N(Ω) is the number of elements scattered in the Ω direction
per unit solid angle per unit time
Number scattered into dΩ:
dσ
N(Ω) dΩ = N 2π sin θ dθ.
dΩ
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 Key Definitions

Equate the two:

dσ
N 2πb db = N 2π sin θ dθ.
dΩ
Simplify:
dσ b db
= .
dΩ sin θ dθ

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 Example: Hard Sphere Scattering

Scattering by a Rigid Elastic Sphere

Consider a particle scattering off a rigid sphere of radius a.
Impact parameter:
   
π−θ θ
b = a sin = a cos .
2 2
Differentiate:
    
db 1 θ db a θ
= a − sin =⇒ = sin .
dθ 2 2 dθ 2 2

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 Example: Hard Sphere Scattering

Differential Cross Section for Hard Sphere

Substitute into the cross-section formula:

D cos 2θ

 
dσ b db D θ
= = · sin .
dΩ sin θ dθ sin θ 2 2

Simplify using sin θ = 2 sin 2θ cos 2θ :

D cos 2θ · D2 sin 2θ



dσ D2
= = .
2 sin 2θ cos 2θ



dΩ 4

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 Example: Hard Sphere Scattering

Total Cross Section for Hard Sphere

Total cross section:

Z Z π Z 2π 2
dσ D
σ= dΩ = sin θ dϕ dθ.
dΩ 0 0 4

Integrate:
π
D2 D2
Z
σ= · 2π sin θ dθ = · 2π · 2 = πD 2 .
4 0 4

This matches the geometric cross section of a sphere of radius a.

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 Example: Hard Sphere Scattering

After applying the assumption of molecular chaos, we substitute:

f2 = f1 (⃗ ⃗1 , t)f1 (⃗
p1 , q ⃗1 , t)
p2 , q

Final equation:
  Z
∂ ∂U ∂ p⃗1 ∂ dσ
+ · + · f1 = − d 3 p̃2 dΩ |⃗v1 − ⃗v2 |
∂t ∂⃗q1 ∂⃗ p1 m ∂⃗ q1 dΩ
p′, q p′, q
 
× f1 (⃗ ⃗1 , t)f2 (⃗ ⃗1 , t) − f1 (⃗ ⃗1 , t)f2 (⃗
p1 , q ⃗1 , t) .
p2 , q (1)

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 Example: Hard Sphere Scattering

Heuristic Explanation

LHS: Streaming terms describing motion in external potential U

RHS: Collision terms:
|⃗v2 − ⃗v1 |: flux of incident particles
|dσ/dΩ|: kinematic factor
f1 (⃗
p1 )f1 (⃗
p2 ): joint probability
Two terms:
Subtraction: probability of particles scattering out
Addition: probability of particles scattering in

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