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Basic Concepts of Statistical Mechanics 12,29
The Most Probable Distribution To know the most probable distribution, it is more
convenient to maximise In Q instead of Q. Therefore, we set
5(nQ)=0 (12.43)
subject to the constraints that the total number of particles in and total energy of the system
are conserved:
N=n, +n, +n, +...=3n, =constant
E=n be +n, €, +ny€; +...= Dn, €; =constant
In the differential form, we can rewrite these constraints as
Yon, =0 (12.44a)
and ‘
Ledn, =0 (12.446)
1, Maxwell-Boltzmann Statistics We first illustrate the procedure of obtaining the most
probable distribution for Maxwell-Boltzmann statistics. From Eq. (12.37), we recall that
thermodynamic probability is given by
on fH)
‘Taking natural logarithm on both sides, we get
In Qyp = In N!+ YL, In g, - In 7, !]
‘To simplify this expression, we use Stirling’s approximation’ (In x! = x In x - x) since g,
as well as n, are large. This gives
In Qyy =N InN -N + DI, Ing, —n, Inn, +7]
If we now invoke the relation N = Sn,, this expression simplifies to
In Qyp =N InN + Dn, Ing, -n, Inn] (12.45)
We now use the fact that Nis constant and g; is not subject to variation. Therefore, on
differentiating Eq. (12.45) with respect to n, we can write
6 An Qy_)= DSL, In g; —n, Inn]
-sfonme
*For a statistical system, the relative error for n = 100 is just 1%, For n = 6 x 10 the relative error will
be almost insignificant. The McGraw-Hill Companies
12,30 Thermal Physics
For most probable state, we equate 5(In Qyq) = 0. This gives
22} fo
Note that this equation is subject to the conditions expressed in Eqs. (12.44a,b) on
the number of particles in and energy of the system. To relax these constraints, we use
Lagrange’s method of undetermined multipliers, wherein we multiply the two constraints
with constants oc and B, respectively. The resultant expressions are added to Eq, (12.46).
The result is
(12.46)
Lon, [n(-}eae,] (247)
It may be mentioned here that we have absorbed the integer 1 in «x
The coefficients 6n, occurring in Eq, (12.47) are arbitrary and non-zero. Therefore, this
result will hold for each i, only if we have
so that
This can be rewritten as
or
8
exp (a + Be;)
7, exp[—(a + Be) = (12.48)
This result is known as Maxwell—Boltzmann distribution law. Note that we intended to
know the set (n,) which characterises the equilibrium state, But in this process, we have
obtained two unknown constants. We will evaluate these in terms of known quantities a
little later,
Before proceeding further, we would like you to work out a practise problem.
PIIORE EL Starting from Eq, (12.378), derive Eg, (12.48).
2, FermiDirac Statistics For F-D statistics, we write Eq, (12.40) as
In Qgp = Dllng, != Inn, ! In(g, = 7,)!]
Using Stirling’s formula, we can rewrite it as
InQpp = Lg; Ing; — g -(g; —m%) Ing; —m) +g; —H))—m; In-M + Hm)
simplification, we get
In Qep = Lg; Ing, -(g, —,) Ing, —-0,) —, Inn} (12.49)
