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Statistical Description of Systems of Particles
Statistical Description of Systems of Particles
Statistical Description
of Systems of Particles
Discussion of the General Problem
• We’ve reviewed elementary probability & statistics.
• Now, we are ready to talk about
PHYSICS
• In this chapter (& the rest of the course) we’ll combine statistical ideas with the
Schrödinger Equation
[-ћ2/(2m)][(∂2/∂x2) + (∂2/∂y2) + (∂2/∂z2)]ψi(x,y,z) = Eiψi(x,y,z)
Using the boundary condition that ψ = 0 on the box faces, it can be shown that:
ψi(x,y,z) = [8/(LxLyLz)]½sin(nxπ/Lx)sin(nyπ/Ly)sin(nzπ/Lz)
nx, ny, nz are 3 quantum numbers (positive or negative integers).
Then, think of this 2-d phase space as divided into cells of equal area:
qp ≡ ho
ho ≡ small constant with units of angular momentum (or “Action”).
• 2-d phase space cells of area: qp = ho.
• The particle “State” (classical) is specified by stating which cell in phase
space the q, p of the particle is in. Or, by stating that it’s coordinate lies
between q & q + q & that it’s momentum lies between p & p + p.
“State” ≡
phase space cell labeled by
the (q,p) that the particle
occupies.
• This involves the “small” parameter ho, which is somewhat
arbitrary. However, we can use Quantum Mechanics &
the Heisenberg Uncertainty Principle:
“It is impossible to SIMULTANEOUSLY
specify a particle’s position & momentum
to a greater accuracy than qp ≥ ½ћ”
• So, the minimum value of ho is clearly ½ћ.
As ho ½ћ, the classical description of
the State the quantum description. &
becomes more & more accurate.
• Now!! Lets generalize all of this to a
MANY PARTICLE SYSTEM
– 1 particle in 1 dimension means we have to deal with
2-dimensional phase space.
– The generalization to N particles is straightforward, but requires
thinking in terms of very abstract
multidimensional phase spaces.
• Consider a system with f degrees of freedom:
The system is classically described by
f generalized coordinates: q1,q2,q3, …qf.
& f generalized momenta: p1,p2,p3, …pf.
A complete description of the classical “State”
of the system requires the specification of:
f generalized coordinates: q1,q2,q3, …qf.
& f generalized momenta: p1,p2,p3, …pf.
(N particles, 3-dimensions f = 3N!)
• So, now lets think VERY abstractly in terms of a
2f-dimensional phase space
The f generalized coordinates: q1,q2,q3, …qf.
& f generalized momenta: p1,p2,p3, …pf are regarded as a
point in the 2f-dimensional phase space of the system.
2f-dimensional phase space: f q’s & f p’s:
• Each q & each p label an axis (analogous to the 2-d phase space for 1 particle in 1 dimension).
• Again, we subdivide this phase space into small “cells” of
2f-dimensional “volume”:
q1q2q3…qfp1p2p3…p1f ≡ (ho)f
The classical “State” of the system ≡ the cell in this 2f-dimensional phase space the system “occupies”.
• Reif, as all modern texts, takes this viewpoint that the system’s
“State” is described by a 2f-dimensional phase space
≡ “The Gibbs Viewpoint”: the system “State” ≡
the cell in this phase space the system “occupies”.
• Older texts take a different viewpoint
≡ “The Boltzmann Viewpoint”:
In this viewpoint, each particle moves in
it’s own 6-dimensional phase space &
the “State” of the system requires specifying each cell in this phase space the each particle in the system “occupies”.
Summary Specification of the State of the System:
• In Quantum Mechanics:
– Enumerate & label all possible quantum states of the system.
• In Classical Mechanics:
– Specify which cell in 2f-dimensional phase space (all coordinates & momenta of all particles) the system occupies.
As ho → ½ћ the classical & quantum descriptions become the same.
Section 2.2: Statistical Ensemble
• As we know, Statistical Mechanics deals with the behavior of systems of a large number of particles.
• Because the number of particles is so huge, we give up trying to keep track of individual particles. We can’t solve
Schrödinger’s equation in closed form for helium (4 particles), so what hope do we have of solving it for the gas
molecules in this room (10f particles).
• Statistical Mechanics handles many particles by calculating the most probable behavior of the
system as a whole, rather than by being concerned with the behavior of individual particles.
In statistical mechanics, We assume that the more ways there are to
arrange the particles to give a particular distribution of energies, the
more probable is that distribution. (This seems reasonable?)
Begin with an assumption that we believe describes nature.
321 411
312 141
213 114
231 3 ways
123
132 more likely
6 ways
• In principle, the problem of a many particle system is
completely deterministic:
• If we specify the many particle wavefunction Ψ (state) of the system (or
the classical phase space cell) at time
t = 0, we can determine Ψ for all other times t by solving the time-
dependent Schrödinger Equation. & from Ψ(t) we can calculate all
observable quantities.
Or, classically, if we specify the positions & momenta of all
particles at time t = 0, we can predict the future behavior of the
system by solving the coupled many particle
Newton’s 2nd Law equations of motion.
• In general, we usually don’t have such a complete specification of the
system available.
– We need f quantum numbers, but f ≈ 1024!
• Actually, we usually aren’t even interested in such a complete
microscopic description anyway. Instead, we’re interested in predictions
of
MACROSCOPIC properties.
We use Probability & Statistics.
To do this we need the concept of an
ENSEMBLE.
• A Statistical Ensemble is a LARGE number
(≡ N) of identically prepared systems.
– In general, the systems of this ensemble will be in different
states & thus will have different macroscopic properties.
We ask for the probability that a given macroscopic
parameter of interest will have a certain
value.
• A Goal or Aim of Statistical Mechanics is to
Predict this probability
• Example: Consider the spin problem again. But, now, let the system
have N = 3 particles, fixed in position, each with spin = ½
Each spin is either “up” (↑, m = ½) or
“down” (↓, m = -½).
• Each particle has a vector magnetic moment μ. The projection
of μ along a “z-axis” is either:
μz = μ, for spin “up”
μz = -μ, for spin “down”
• Now, put this system into an external magnetic field H.
– Classical E&M tells us that a particle with magnetic moment μ in an external field H
has energy:
ε = - μ∙H
– Let’s combine this with the Quantum Mechanical result:
This tells us that each particle has 2 possible energies:
ε+ ≡ - μH for spin “up”
ε- ≡ μH for spin “down”
So, for 3 particles, the State of the system is specified by
specifying m =
There are (2)3 = 8 POSSIBLE STATES
The Possible States of a 3 Spin System
• This additional information limits the states which are accessible to the system.
• From the table, there are clearly only 3 states which are compatible with
this knowledge.
The system must be in one of the 3 states: (+,+,-) (+,-,+) (-,+,+)
Sect. 2.3: The Basic (or Fundamental)
Postulate of Statistical Mechanics
• Definition:
An ISOLATED
SYSTEM
≡ A system which has no interaction of any kind with the “outside
world”
• This is clearly, an idealization! Such a system has
No Exchange of Energy with the outside world.
The laws of mechanics tell us that the
total energy E is conserved.
E ≡ Constant
• So, an isolated system is one for which
total energy is conserved
• Now, consider an isolated system. The total energy E is constant & the system is characterized
by this energy. So,
All states accessible to it MUST have this energy E.
• For many particle systems, there are usually a HUGE number of states with the same energy.
Question
What is the probability of finding the system in any one of these
accessible states?
• Before answering this, let’s define the term “Equilibrium”.
A System in Equilibrium is one for which the
Macroscopic Parameters characterizing it are
independent of time.
• Now, consider an isolated system in equilibrium:
• In the absence of any experimental data on some specific system properties, all we can
really say about this system is that it must be in one of it’s accessible states (with that
energy).
If this is all we know, we can “handwave” the following:
There is nothing in the laws of mechanics (classical or quantum) which would lead us to suspect that, for an
ensemble of similarly prepared systems, we should find the system in some (or any one) of it’s
accessible states more frequently than in any of the others. So,
E = constant
x
• If we knew the oscillator energy E exactly, the accessible states would be the
points on the ellipse. In practice, we never know the energy exactly! There is
always an experimental error δE.
δE ≡ Uncertainty in the energy. Always assume:
|δE| <<< |E|
• For the geometrical picture in the x-p plane, this means that the energy is
somewhere between 2 ellipses, one corresponding to E & the other corresponding to
E + δE.
≡ “Boltzmann’s H-Theorem”
Gas Vacuum
• Clearly, to calculate this, we need to know both Ω(E) & Ω(E;yk). This
will be discussed in detail!
In principle (if we know the Ω’s) this calculation is easy.
• Example: 3 particles of spin ½ in an external magnetic field again. Suppose that we
know from measurement that the total energy is E = - μH. As we’ve seen, there are
only 3 accessible states for E = - μH. These are: (+,+,-) (+,-,+) (-,+,+).
• Question: What is the probability of finding spin #1 in the “up” position? In this case,
Ω(E) Ω(E = -μH) ≡ 3 and
Ω(E;yk) Ω(E = -μH; spin 1 is “up”) ≡ 2
• So, the probability that spin #1 is “up” is:
P(spin 1 “up”) ≡ (⅔)
• Also, the probability that spin #1 is “down” is:
P(spin 1 “down”) ≡ (⅓)
• So, we can find answers to questions like: What is the Mean (average)
magnetic moment of spin # 1?
<μz> = (⅓)μ
Section 2.5: Behavior of the Density of States
• We’ve just seen that the probability that a system parameter y has a value yk is:
P(y = yk) ≡ [Ω(E;yk)/Ω(E)] Ω(E) ≡
E & E + δE.
number of accessible states with energy between
To do probability calculations,
we need to know the E dependence of Ω (E).
• Goal of this discussion: APPOXIMATE the E dependence of Ω(E).
– Discussion will not be mathematically rigorous. More of a “handwave”.
• Macroscopic System, f degrees of freedom, f is huge! f ~ 1024.
• The energy is in range E to E + δE. Of course, Ω(E) δE. Extrapolating the
discussion of the 1d oscillator,
Ω(E) ~ the volume of phase space in this energy range. Define Ω(E)
≡ ω(E)δE. ω(E) ≡ Density of states
• Our Goal: ESTIMATE E dependence of Ω(E) (or ω(E)).
~ How many accessible states are there for a macroscopic
(f ~ 1024) system at energy E?
– We aren’t interested in exact results.
– We want an order of magnitude estimate!!
– The result is an abstract, but very significant result.
• Let Φ(E) ≡ total # of quantum states for all energies E´ ≤ E.
• Consider 1 “typical” degree of freedom. ε ≡ energy associated with that degree of
freedom. Let φ(ε) ≡ total # of quantum states for this degree of freedom.
• In general, φ(ε) increases with increasing ε. So, we can write:
φ(ε) εα ( α ~ 1) (1)
φ(ε) ε (1)
• Now, for the system, replace the energy E by an “average energy” for a system of f
degrees of freedom:
ε (E/f) (2)
• f degrees of freedom & φ(ε) states associated with each one.
The total # of states associated with f degrees of freedom ≡ the product of the
# associated with each one: Φ(E)
[φ(ε)]f (3) Now, use (1), (2), & (3) together:
The total # of states for all energies E´ ≤ E is roughly:
Φ(E) [φ(ε)]f [E/f]f Ef ≡ AEf (4)
A = constant
Ω(E) ≡ # accessible states with energy between E & E + δE
So, write: Ω(E) ≡ Φ(E + δE) - Φ(E); δE <<< E Now,
expand Φ in a Taylor’s series & keep only the lowest order term:
Ω(E) Ef δE (f ~ 1024)
Ω(E) is a RAPIDLY
(!!) increasing function of
E!!!!!
• Briefly look at some numbers with powers of 10 in the exponent to get a “feel for the “bigness” of
Ω(E) Ef :
1. The age of the Universe in seconds is “only” 1018 s!
1 with 18 zeros after it!
2. The Universe Volume divided by volume of a grain of sand
is “only” 1090! 1 with 90 zeros after it!
3. If f ~ 1024: By what factor does Ω (E) change when E changes by only 1%?
Let r ≡ [Ω (E + 0.01E)/Ω (E)] = (1.01)f, f ~ 1024
Evaluate r using logarithms: log10(r) = 1024log10(1.01) 4.32 1021
So, r 10x, where x 4.32 1021,
r ~ 1 with 4.32 1021 zeros after it!
Now, consider the same problem again, but let E increase by only 10-6E:
We get r 10y, where y = 4.34 1017,
r ~ 1 with 4.34 1017 zeros after it!
• Finally, consider 2 numbers:
C = 10u, u = 1024, D = 10v, v = 2 1024
• Finally, consider 2 numbers:
C = 10u, u = 1024 , D = 10v, v = 2 1024