Derivation of The Boltzmann Distribution Law

20.110J / 2.772J / 5.
601J
Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field
Lecture 14
5.60/20.110/2.772
Why works for large N

Derivation of the Boltzmann Distribution Law
Partition Function
Why works for large N

We have seen that a system will vary its degrees of freedom in order to maximize and thus S. A
system has a higher probability of being in a state due to it being more probable. This allows us to
simply count states and see which one is more likely.
The lattice model of mixing gases had only N=8 particles. Is this approach still justified when we look
at a larger number of particles, like NA? It turns out the most probable state at low N becomes even
more likely at very high N.
Consider: coin flips
nH
4
3
2
1
0
S =kln
4!
N!
=
=1
n!( N n )! 4!0!
4!
==
=4
3!1!
4!
==
=6
2!2!
4!
==
=4
1!3!
4!
==
=1
0!4!
0
1.386k
1.792k
1.386k
0
Then do for N = 10, 100, 1000

max
N=4
max
max
10 n
100
N=1000
becomes increasingly narrower as N. Compare numerically:

1
50
max
N=10
N=100
500
1000
20.110J / 2.772J / 5.601J

Lecture 14
(5,10 ) =
(2,10 ) =
5.60/20.110/2.772
10!
= 252
5!5!
10!
= 45
2!8!
(50,100 ) =
5.6X more likely

(20,100 ) =
100!
= 1 10 29
50!50!
100!
= 5 10 20
20!80!
109X more likely!
Even though the process is totally random: If the number of trials N is large enough, the composition
of the outcomes becomes predictable with great precision.
This allows us to better predict the most probable state!
maximizing = maximizing S
Derivation of the Boltzmann Distribution Law

Microscopic definition of entropy:
t
S = k p j ln p j
i =1
What probability distribution (set of pjs) maximizes S?
S
=0
p j
for all j
constraint that probabilities sum to 1:
=1
j =1
t
dp
=0
j =1
Utilize Lagrange multipliers to solve this problem. We add the constraint to the equation we are
trying to maximize with a multiplier, . Then when we maximize the resulting equation the value of
is determined. i.e., solving the set of equations:
j =1
p j
t
dp j = 0
for all j
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Lecture 14
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Plug in definition of S (pj):

t
t

k p j ln p j p j = 0
p j
j
j =1
Take the derivative:
k (ln p j + 1) = 0
ln p j =
pj = e
1
k
Divide pi by 1 to get rid of :
pj
t
pi
i =1
te
1
t
This says: Flattest probability distributions have highest S. This is something we already knew.
Now, what happens when we impose a constraint on the system? i.e., you have a given temperature,
and can sum up to a particular total energy. This is a more realistic problem to solve.
Lets put this into practice with an example.
Simple model to illustrate: 4 bead polymer
-0
compact
open
The polymer can assume multiple configurations. Well label one end atom so that it is distinguishable
from the other atoms in the chain. The polymer is stabilized when in compact configuration by energy
from open state. This is represented by the dashed line. This is a simple model utilized by those
studying protein folding as it can represent the configurations of a protein in the folded and unfolded
states. It represents a polypeptide chain that has only 4 amino acids, and a great simplification of real
proteins in that the chain can assume only a small number of conformations: one compact and four
open.
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Lecture 14
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native
denatured
One end bead is labeled so that it is distinguishable from other end.

a microstate
1st excited
state
E=
a macrostate
ground state
E=0
microstate: a possible configuration. snapshot. A measurement averages over several

microstates
macrostate: a collection of microstates with the same energy
Define the E=0 state as the compact form, where the chain is stabilized by some energy relative to
the open state due to the interaction between bead 1 and bead 4.
Degree of freedom: physical conformation of the chain and the energy of each conformation, or
microstate.
What is the probability distribution that minimizes or maximizes a relevant thermodynamic quantity?
What happens if we try do this in real laboratory conditions? (T,V,N) or (T,P,N) controlled.
Lets say we have (T,V,N) constant, making A what we want to minimize.
dA = dU = TdS
at equilibrium:
dA = 0
Goal: Get dU and dS and solve for pj that makes dA = 0.
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Lecture 14
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Differentiate with respect to pi

t
dS = k (1 + ln p j )dp j
j =1
Recall definition of an average value:

t
E = pjEj
j =1
dU = d E = ( p j dE j + E j dp j )
j =1
Energy levels do not depend on T. pj, or how they are populated, do.
t
dU = d E = (E j dp j )
j =1
dA = d E TdS = 0
use the constraint:
t
=1
j =1
Which allows us to use the Lagrange Multiplier

t
dp j = 0
j =1
Plug everything back into dA equation:
dA = d E TdS = 0
t
t
= E j dp j T k (1 + ln p j )dp j + dp j = 0
j =1
j =1
j =1
adding 0
group dpj terms:
t
dA = E j + kT (1 + ln p j ) + dp j = 0
j =1
must =0
5
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Lecture 14
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ln p*j =
Ej
kT
1
kT
pj*= set of pj that satisfies dA=0
p*j = exp j exp

1
kT
kT
Well eliminate from the equation by using
t
=1
j =1
First, sum both sides:
Ej

exp

=
=
1
1
exp
p
kT
j =1
j =1
kT
t
*
j
E
t

1 exp j
1 = exp
kT j =1
kT
Rearranging the last expression
exp
1
t
Ej
kT
exp
kT
j =1
Plug this back into pj*:
Ej
exp
kT
p *j = t
Ej
exp
j kT
Ej
exp
kT
=
Q
Boltzmann Distribution Law
pj is the probability that the systems is in the Ejth energy level
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Lecture 14
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We have defined the denominator as Q, the partition function
1
t
Ej

exp
j =1
kT
We arrived here by finding the probability distribution, or set of pjs, that minimizes the free energy.
What does it say?
When you are trying to maximize entropy, minimize energy: more particles like to have lower
energies. Particles populate relatively low Ej apiece
Probability distributions have an exponential form when you place constraints on them (not flat,
like for the case of no constraints)
Relative populations of two levels:
pi*
(Ei E j )
=
exp
kT
p *j
If j higher than i, then Ei-Ej<0 (negative)

so exp (+)
pi/pj >1, more in ith level.
Note: Particles do not have a preference for the lower energies, there is just a greater number of
ways to arrange the particles so that they distribute the E.
For a given Etot, can arrange particles in several ways to achieve Etot. However, the Boltzmann
Distribution Law says that the left hand situation is much more probable as it has the higher entropy.
many possible
arrangements
few possible
arrangements
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Lecture 14
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What is the partition function?

In our derivation of the Boltzmann equation, the partition function, Q, came out.
Ej
Q exp
kT
j =1
Q describes how the particles are partitioned throughout accessible states. It is a number. Note that
Q is temperature dependent!
In simpler terms: Q tells you the number of states that are effectively accessible to the system at a
given temperature.
Qualitatively:
If you have t energy levels:

Et
....
E3
kT
(many states
accessible)
E2
E1
(few states
kT accessible)
E0
Ej
E
E
E
E
= exp 0 + exp 1 + exp 2 + + exp t
Q exp
kT
kT
kT
kT
j =1
kT
t
Ej/kT factor: magnitude of Ej relative to kT is the relevant number.

8
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Lecture 14
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Units of kT: [J] (energy)

Lets look at two limits:
a) T (hi temperature) OR Ej0 (small energy spacing)
then Ej/kT0
E
exp j
kT
1
1
p*j = t
=
= = p *j
E (1 + 1 + 1) t
j exp kTj
this means: all states are accessible. Note that
Qt
b)T 0 (low temp) OR Ej (big energy spacing)
then Ej/kT
p *j =0 =
1
= 1 = p *j =0
(1 + 0 + 0)
p *j =rest =
0
= 0 = p *j =rest
(1 + 0 + 0)
this means: only ground state accessible.
Q 1
Now lets do it again for our 4 bead polymer:
E=
E=0
We still need to account for one more thing:

Degeneracy, g of upper the macrostate--there are four microstates.
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Lecture 14
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l max
El
g (E )exp kT
l
l are the levels. gl=0 = 1, gl=1= 4

Q = 1 exp( 0 ) + 4 exp
= 1 + 4 exp
kT
kT
Q(T):
At low T, Q=1 (lowest state accessible)
At high T, Q=5 (all states accessible)
and also pl (T).
p compact
p open
0
kT
1 e
=
Q
4e
=
Q
kT
pcompact =1
popen =4/5
1
=
Q
pl
pcompact =1/5
popen =0
T
This is a unfolding or a denaturation profile for a polymer or protein, etc. Experiments: Fix T,
measure popen vs pcompact.
Why are we so interested in Q? We will re-derive thermodynamic properties in terms of Q. This is
the link between the microscopic and macroscopic descriptions.
Interesting side note: Calculate S of unfolding using S=k ln
Sclosed = k ln 1 = 0
Sopen = k ln 4
S = +
This says that the protein will want to unfold, based only on entropy. However, this model does not
account for things like interaction with the water molecules around the protein, which order around the
chain.
10

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20.110J / 2.772J / 5.

Why works for large N

Why works for large N

Then do for N = 10, 100, 1000

becomes increasingly narrower as N. Compare numerically:

20.110J / 2.772J / 5.601J

5.6X more likely

109X more likely!