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Part II

Y Y Shan

Statistical thermodynamics—The Microscopic theory

The classical theory of thermodynamics leaves certain questions unanswered:

The statistical theory can answer all these.

The Macrostates and Microstates of a thermodynamic system:
Classical thermodynamics describes macroscopic systems in terms of a few
variables (state functions).

A macrostate of a system refers to its macroscopic properties

such as temperature and pressure, etc.
But such a system is really made of millions of atoms, so a much richer
description must be possible in principle: we could specify the quantum states of all
individual atoms. This suggests we can calculate the macro-state of a system by
averaging over the corresponding huge amount of microstates of the system. We can
derive thermodynamics from the quantum behavior (quantum states) of atoms and
In Statistical thermodynamics, a microstate of a system describes a specific
detailed microscopic configuration of a system.

The crucial link from microscopic to

macroscopic properties is as follows. If the value of some quantity

in the


microstate is X i , and the probability that the system is in that microstate is pi , then the
value of

in the macrostate is the average :

〈 X 〉 = ∑ pi X i



If a system contains many micro- particles. Y Y Shan Background knowledge and concepts for statistical thermodynamics A (quantum) State of a particle: For micro-particles. such as “2-dots” state? If a “particle” is a token (blue on one side and green on the other). the system will have many microstates. all the six states are equally probable. it has two states: state “blue” and state “green”. the probability of getting a “blue” state (or a “green” state) is ½. A Microstate of a system (consists of many particles): defined in terms of the current behavior of all the constituent particles(atoms). If a “particle” were a die. Example (i): A system has two “particles”—two dice (distinguishable) The combination of the states from each “particle” forms microstates of the system of two-dice. 2.Thermodynamics Chapter 6 1. Given one toss of a token. they have quantum states. obviously it has six states: For the throw of a single die. Given one throw of a die. ψ n . depending on the combination of the states of each individual particle. for instance. such as: AP3290 are five different 83 . described by their wave functions. what is the probability of getting a state.

Now we toss them and place them on a 6 by 6 checkerboard. the system is equally likely (equal probability) to be found in any of its accessible microstates. i. Ω Ω Ω 1 ∑ p = ∑ Ω =1 i i i 84 .Thermodynamics Y Y Shan microstates of the “2-particle” system. Its total number of the microstates of the system is: Ω = P61 ⋅ P61 = 6 × 6 = 36 where the distribution showing total-2-dots (T2) of the system has one “microstate”. 26 3. We use Ω for the number of such microstates. each microstate of the system has the same probability to be observed.. The principle of equal a priori probabilities The fundamental postulate (assumption) in statistical mechanics is the principle of equal a priori probabilities.e. The total number of microstates of the system: Ω = P21 ⋅ P21 ⋅ K ⋅ P21 = (P21 ) = 2 26 = 6. the distribution showing total-6-dots (T6) has five “microstates” Example (ii): A system having 36 chips (indistinguishable—identical chips): one side is blue and the other is green. Many different patterns are possible to be generated. It states: An isolated system in equilibrium.87 × 1010 . so the probability of the system being in any one microstate is pi = AP3290 1 . Or a system in equilibrium does not have any preference for any of its available microstates. Each pattern (formation) stands for a microstate of the system. the following shows six possible microstates of the system.

Thermodynamics Y Y Shan Examples: (i) For the two-dice system. What is the probability of throwing to get a microstate of “2-dots + 3-dots” ? The probability of the system at any microstates: is same and equal to: Example (ii): 1 1 = Ω 36 For the 36-pieces counter system: the following shows six microstates of the system. Each microstate of the system is equally likely to occur. The probability of the system accessing to any microstate is same and equal to: pi = AP3290 1 1 = 36 = 1.46 × 10 −11 Ω 2 85 .

AP3290 86 . each microstate of the distribution has something in common.1 Distribution. It is concluded that the more microstates a distribution has. A distribution has maximum number of microstates is called a most probable distribution. Distribution. The probability of getting the distribution consisting of T4 states is: 4 × (1 / 36) = 0. If the condition set for the microstates is: the total “dots” must be seven (T7). etc. i. and Distributions in statistical physics 4. therefore the number of microstates of the distribution will be 4. From the principle of equal a priori probabilities. There are 6 ways (6 states) to get a total of seven-dots (T7). the number of microstates for a distribution . the probability of showing each microstate is same and equals to 1/36 . having N particles) is a group of microstates which all satisfy a particular condition (or constrain).111 . then the total number of microstates of the distribution is 6.) Example: For the system of two-dice If a condition set for the microstates is: the total “dots” must be five (T5).167 .and most probable distribution The concept of distribution: A distribution (of a system. These conditions can be: fixed total energy of all microstates of a distribution.e. particular particle characters (distinguishable. but only 1 way (1 state) to get two-dots (T2). indistinguishable. the higher probability the distribution will appear.Thermodynamics Y Y Shan 4. The probability of getting the distribution consisting of T7 states is the highest: 6 × (1 / 36) = 0.

2 System with Distinguishable or indistinguishable particles Example (i) : the 36-counters system: Looking into a particular distribution (of the system).. what is the total number of microstates for this particular distribution. n = 15 .71993 × 10 41 (b) Indistinguishable particles: If “Green”s and “Blue”s can not be distinguished. ⋅ 2 ⋅1 = 3. (a) Distinguishable particles: If those “Green”s and those “Blue”s can be distinguished. what is the total number of microstates for this particular distribution.. without caring about the ordering in each group. where all its microstates have 15-Green? This is the common problem of splitting a group of into two smaller groups. and the number of ways of doing it is Ω Ind = C Nn = AP3290 N! n !( N − n)! 87 . N = 36. of witch all the microstates have 15-Green (and 21-Bluie)? There are ways of putting distinguishable counters Ω dis = N != 36!= 36 ⋅ 35 ⋅ . of which all its microstates are under the constraint of having “15-Green” (the rest “21-Blue”). of and N − n .Thermodynamics Y Y Shan 4.

. Here. 15 9 For . The numbers C N = N! are called the binomial coefficients. and ( N − n)! ways of arranging the blues.Thermodynamics There are Y Y Shan ways of putting counters are green. 10 8 It is found that: For 18 9 . there are distinguishable counters.075 × 10 . so the total is Ω = C36 = 36!/(15!⋅12!) = 5. is the the maximum. Ω = C36 = 36!/(18!⋅18!) = 9.g. then the two “particles” (dice) are said to be distinguishable. We call a distribution which has maximum number of microstates the “most probable distribution”.542 × 10 . for e. n!( N − n)! since they enter the binomial expansion. Hence the above distribution with 18-green among 36 in total is the most n probable distribution. (a) Distinguishable particles: If . AP3290 88 . Example (ii) two-dice system. For there are only Ω = C36 = 36!/(10!⋅26!) = 2.568 × 10 . However if of the ways of arranging the green counters among themselves without changing the pattern.

The total microstates of the system from all distributions (11) are 36. the number of microstates for the distribution of “total-dots-is-six” will be reduced from 3 to 2.g. its microstates is 6. then the two “particles” (dice) are said to be indistinguishable. Now the number of microstates of the “total-dots-is-seven” distribution reduces 6 to 3. for e.Thermodynamics Y Y Shan As for the particular distribution: “total-dots-is-seven”. (b) Indistinguishable particles: If. (c) If two indistinguishable particles can not have the same individual states (particles are so called Fermions).. which is the most probable distribution. . while the total number of microstates of the system decreases from 36 down to 21.g. While. AP3290 89 .. for e. Now the total number of microstates of the system further reduced from 21 to 15.

Fermi–Dirac distribution.Thermodynamics Y Y Shan 4.3 Distributions in particle statistics: For those examples in 4. concerning energies of individual states. atoms etc.2. and Bose–Einstein distribution (particles are in distinguishable). in statistical thermodynamics. are namely Maxwell– Boltzmann distribution (particles are distinguishable). these will be quantum states. These distributions.) are not assigned (or taken into account). the energies of each particle at its different individual states (for real particles. However. energies of (quantum) states of individual particles must be under consideration when discussing the energies of microstates of different distributions from systems consisting of real particles. AP3290 90 . such as electrons. Therefore. the total energy of a system containing large amount of particles is very important.

This result is called a "combination". 0!≡ 1 ∏ ai = a1 ⋅ a2 ⋅ . then the number of ways you can pick a number r of them (r < N) is given by the permutation relationship: PNr = n! ( N − r )! For example if you have six persons for tennis. ⋅ ai i (iii) Permutations and Combinations If you have a collection of N distinguishable objects.e. because it treats the match of A vs B as distinct from the match of B vs A for players A and B.. r). Some mathematics: (i) (ii) n!= n ⋅ (n − 1) ⋅ (n − 2) ⋅ .Thermodynamics Y Y Shan 5... then the number of pairings for singles tennis is P62 = 6! = 6 ⋅ 5 = 30 (6 − 2)! But this really double counts.. If you don't want to take into account the different permutations of the elements (i. The combination relationship is C Nr = N! ( N − r )!r! The number of tennis matches is then the combination C62 = AP3290 6! 6⋅5 = = 15 (6 − 2)!2! 2 91 . ⋅ 2 ⋅ 1 . then you must divide the above expression by the number of permutations of r (here r=2).