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Macrostates & Microstates 1
Macrostates & Microstates 1
2 )
The past three lectures: we have learned about thermal energy, how it is
stored at the microscopic level, and how it can be transferred from one
system to another. However, the energy conservation law (the first law of
thermodynamics) tells us nothing about the directionality of processes
and cannot explain why so many macroscopic processes are
irreversible. Indeed, according to the 1st law, all processes that conserve
energy are legitimate, and the reversed-in-time process would also
conserve energy. Thus, we still cannot answer the basic question of
thermodynamics: why does the energy spontaneously flow from the hot
object to the cold object and never the other way around? (in other words,
why does the time arrow exist for macroscopic processes?).
For the next three lectures, we will address this central problem using the
ideas of statistical mechanics. Statistical mechanics is a bridge from
microscopic states to averages. In brief, the answer will be: irreversible
processes are not inevitable, they are just overwhelmingly probable.
This path will bring us to the concept of entropy and the second law of
thermodynamics.
i Microstates and Macrostates
The evolution of a system can be represented by a trajectory
2
1 in the multidimensional (configuration, phase) space of micro-
parameters. Each point in this space represents a microstate.
During its evolution, the system will only pass through accessible microstates
the ones that do not violate the conservation laws: e.g., for an isolated
system, the total internal energy must be conserved.
Microstate: the state of a system specified by describing the quantum state
of each molecule in the system. For a classical particle 6 parameters (xi, yi,
zi, pxi, pyi, pzi), for a macro system 6N parameters.
The statistical approach: to connect the macroscopic observables
(averages) to the probability for a certain microstate to appear along the
systems trajectory in configuration space, P( 1, 2,..., N).
Macrostate: the state of a macro system specified by its macroscopic
parameters. Two systems with the same values of macroscopic parameters
are thermodynamically indistinguishable. A macrostate tells us nothing about a
state of an individual particle.
For a given set of constraints (conservation laws), a system can be in many
macrostates.
The Phase Space vs. the Space of Macroparameters
some macrostate
P numerous microstates
in a multi-dimensional
T
configuration (phase)
space that correspond
V the same macrostate
the surface i
defined by an
equation of i
states 2
1
2
1
i etc., etc., etc. ...
i
2
2 1
1
Examples: Two-Dimensional Configuration Space
motion of a particle in a
one-dimensional box
K=K0
-L L
0 K
Macrostates are characterized by a
single parameter: the kinetic energy K0
-L L x
x px
-px
This approach will help us to understand why some of the macrostates are
more probable than the other, and, eventually, by considering the interacting
systems, we will understand irreversibility of processes in macroscopic
systems.
Probability theory is nothing but common sense
Probability reduced to calculations Laplace (1819)
An event (very loosely defined) any possible outcome of some measurement.
An event is a statistical (random) quantity if the probability of its occurrence, P, in the
process of measurement is < 1.
The sum of two events: in the process of measurement, we observe either one of the
events.
Addition rule for independent events: P (i or j) = P (i) + P (j)
(independent events one event does not change the probability for the
occurrence of the other).
Example: What is the probability of the same face appearing on two successive
throws of a dice?
The probability of any specific combination, e.g., (1,1): 1/6x1/6=1/36 (multiplication rule) .
Hence, by addition rule, P(same face) = P(1,1) + P(2,2) +...+ P(6,6) = 6x1/36 = 1/6
E
A particular microstate (....)
is specified if the directions of all spins are
B E2 = + B specified. A macrostate is specified by the total
# of dipoles that point up, N (the # of dipoles
an arbitrary choice 0 that point down, N = N - N ).
of zero energy
N - the number of up spins
E1 = - B N N N
N - the number of down spins
M= 2 0 0 - 2
In zero field, all these microstates have the same energy (degeneracy). Note
that the two microstates with M=0 have the same energy even when B0:
they belong to the same macrostate, which has multiplicity =2. The
macrostates can be classified by their moment M and multiplicity :
M= 2 0 - 2
= 1 2 1
M= 3 - - - -3
M= 3 - -3
macrostates:
= 1 3 3 1
The Multiplicity of Two-State Paramagnet
Each of the microstates is characterized by N numbers, the number of
equally probable microstates 2N, the probability to be in a particular
microstate 1/2N.
For a two-state paramagnet in zero field, the energy of all macrostates is
the same (0). A macrostate is specified by (N, N). Its multiplicity - the
number of ways of choosing N objects out of N :
N N 1 N N 1 N 2
( N ,0) 1 ( N ,1) N ( N ,2) ( N ,3)
2 3 2
N N 1 ... N n 1 N! n ! n factorial =
( N , n)
n ... 3 2 1 n !n 1! 12....n
0 ! 1 (exactly one way to
arrange zero objects)
The multiplicity of a N! N!
macrostate of a two-state ( N , N )
paramagnet with (N, N): N! N! N! ( N N )!
Math required to bridge the gap between 1 and 1023
Typically, N is huge for macroscopic systems, and the multiplicity is
23
unmanageably large for an Einstein solid with 1023 atoms, ~ 10 10
One of the ways to deal with these numbers to take their logarithm [ in
fact, the entropy S of the macrostate kB ln of the macrostate ]
thus, we need to learn how to deal with logarithms of huge numbers.
e ln x x
ln xy ln x ln y ln x / y ln x ln y
ln x y ln x
y
e 10
x x / ln10
~ 10 0.43 x
Stirlings Approximation for N! (N>>1)
Multiplicity depends on N!, and we need an approximation for ln(N!):
N
lnN! ln1 ln2 ln3 lnN ln x dx x ln x x 1 N ln N N
N
1
N
ln N! N ln N N N
or N !
e
More accurately: N
N
N! N e N N
2N 2N
e
Check:
ln N ! N ln N N ln N ln 2 N ln N N
1 1
2 2
because ln N << N for large N
The Probability of Macrostates of a Two-State PM (B=0)
( N , N ) ( N , N ) ( N , N )
P( N , N )
# of all microstate s ( N , all N ) 2N
N! N N e N
P( N , N )
N !N N !2 N
N e N N e
N N N N N N N
2
NN
- as the system becomes larger, the
N N N 2 N
N N N
P(N,N) graph becomes more
sharply peaked:
N =1 (1,N) =1, 2N=2, P(1,N)=0.5
N N Nn
0 1 0 0.51023 1023
(http://stat-www.berkeley.edu/~stark/Java/BinHist.htm#controls)
Multiplicity and Disorder
In general, we can say that small multiplicity implies order, while large multiplicity
implies disorder. An arrangement with large could be achieved by a random
process with much greater probability than an arrangement with small .
small large
The Einstein Model of a Solid
In 1907, Einstein proposed a model that reasonably predicted the thermal
behavior of crystalline solids (a 3D bed-spring model):
a crystalline solid containing N atoms behaves as if it contained
3N identical independent quantum harmonic oscillators, each of
which can store an integer number ni of energy units = .
We can treat a 3D harmonic oscillator as if it were oscillating
independently in 1D along each of the three axes:
1 2 1 2 1 1 1 1 1 1
E mv k r mvx k x 2 mvy k y 2 mvz k z 2
2 2 2
classic:
2 2 2 2 2 2 2 2
1 1 1 3 1
quantum: Ei ni , x ni , y ni , z ni
2 2 2 i 1 2
all oscillators are identical, the energy quanta are the same
dU/dT,
solid
The Einstein Model of a Solid (cont.) J/Kmole
Lead
At high T >> (the classical limit of large ni):
26.4
Gold 25.4
3N
1 dU
U ni 3 N (2) k BT 3Nk BT 3Nk B Silver
2 dT 25.4
i 1
(1,0) =1
(1,1) =3
(1,3) =10
(1,2) =6
The Multiplicity of Einstein Solid
The multiplicity of a state of N oscillators (N/3 atoms) with q energy quanta
distributed among these oscillators:
( N , q)
q N 1 !
q !( N 1) !
Example: The multiplicity of an Einstein solid with three atoms and eight units of
energy shared among them
(9, 8)
8 9 1 !
12,870
8!(9 1) !
Multiplicity of a Large Einstein Solid (kBT >> )
q = U/ = N - the total # of quanta in a solid.
= U/( N) - the average # of quanta (microstates) available for each molecule
q N 1 ! q N !
ln ( N , q) ln
ln ln q N ! ln q ! ln N!
q ! ( N 1)! q ! N !
Stirling : lna! a ln a a
q N ln q N q N q ln q q N ln N N
q N ln q N q ln q N ln N
high temperatures: N
ln ( N , q) q N ln q q ln q N ln N
(kBT >> , >>1, q >> N ) q
N N N2 q
ln( q N ) ln q1 ln q N ln q N N ln N N ln N
q q q N
N N Einstein solid:
q
eU
e e (U , N )
N ln eq
( N , q) e f (N ) U
N N N N
(2N degrees
N N of freedom)
q N
low temperatures: eN e
(kBT << , <<1, q << N )
( N , q) (Pr. 2.17)
q
Concepts of Statistical Mechanics
1. The macrostate is specified by a sufficient number of macroscopically
measurable parameters (for an Einstein solid N and U).
2. The microstate is specified by the quantum state of each particle in a
system (for an Einstein solid # of the quanta of energy for each of N
oscillators)
3. The multiplicity is the number of microstates in a macrostate. For
each macrostate, there is an extremely large number of possible
microstates that are macroscopically indistinguishable.
4. The Fundamental Assumption: for an isolated system, all
accessible microstate are equally likely.
5. The probability of a macrostate is proportional to its multiplicity. This
will sufficient to explain irreversibility.