2A_FA21_Stat2PHY467_02_BY_M.

Jamil

Example: Find the electronic partition of H2 at 300 K

Solution:The lowest electronic energy level of H2 is near -32 eV and the next level is about 5 eV higher.
Taking - 32 eV as the zero (or reference value of energy),
5eV
Zelec = qelec = e0 + e kB T ; At 300K = 0:02eV = e0 + e 200
1:0

The physical means that only the ground electronic state is generally accessible at room temperature.
PARTICLE IN A THREE-DIMENSIONAL BOX(A RECAP):
Let us explore the workings of wave mechanics in three dimensions through the example of a particle
con…ned to a cubic “box.”The box has edge length L and occupies the region 0 < (x; y; z) < L. We assume
the walls of the box are smooth, so they exert forces only perpendicular to the surface, and that collisions
with the walls are elastic. At each collision, the
component of particle momentum normal to the wall is reversed (changes sign), while the other two
components of momentum are una¤ected. Thus, the collisions preserve the magnitude of each momentum
component, in addition to the total particle energy. These four quantities, px , py , pz , and E, then, are
constants of the classical motion, and it should be possible to …nd quantum states for which all of them
are sharp. The wavefunction in three dimensions is a function of r and t. Again the magnitude of (r; t)
determines the probability density
P (r; t) = j (r; t)j2
, which is now a probability per unit volume. Multiplication by the volume element dV(dx dy dz) gives the
probability of …nding the particle within the volume element dV at the point r at time t.

P (r; t) = j (r; t)j2

Since our particle is con…ned to the box, the wavefunction must be zero at the walls and outside. The
wavefunction inside the box is found from Schrödinger’s equation,

}2 r2 @
+ U (r) = i} (1)
2m @t
2 2
We see that @ =@x in the one-dimensional case is replaced in three dimensions by the Laplacian,

@2 @2 @2
r2 = + + (2)
@x2 @y 2 @z 2
where U(r) is still the potential energy, a function of all the space coordinates: U(r) U(x, y, z). The
Laplacian together with its multiplying constant is just the kinetic energy operator.

}2 2 }2 @ 2 }2 @ 2 }2 @ 2
r = + + (3)
2m 2m @x2 2m @y 2 2m @z 2
= [Kx ] + [Ky ] + [Kz ]

Stationary states are those for which all probabilities are constant in time, and are given by solutions to
Schrödinger’s equation in the separable form,

i!t
(r; t) = (r)e (4)
With this time dependence, the right-hand side of Equation 1 reduces to }! (r) , leaving (r) to satisfy
the time-independent Schrödinger equation for a particle whose energy is E, :

}2 2
r (r) + U (r) (r) = E (r) (5)
2m
In 1-D, particle is free inside the box, potential energy U(r)= 0 for 0<( x, y, z)< L. In this case the
spatial wavefunction also is separable; with U(r)= 0,
 (r) = (x; y; z) = 1 (x) 2 (y) 3 (z) (6)
Substituting Equation 6 into Equation 5 and dividing every term by the function (x, y, z) gives (for
U(r) =0),

}2 d 2 }2 d 2 }2 d 2
1 (x) 2 (y) 3 (z) 1 (x) 2 (y) 3 (z) 1 (x) 2 (y) (z) = E 1 (x) 2 (y) 3 (z)
(7)
2m dx2 | {z } 2m dy 2 | {z } 2m dz 2 | 3{z }
} 2 d 2 }2 d2 }2 d2
1 (x) 2 (y) 3 (z) = E
2m 1 (x) dx2 2m 2 (y) dy 2 2m 3 (z) dz 2

The independent variables are isolated: the …rst term on the left depends only on x, the second only on
y, and the third only on z. To satisfy the equation everywhere inside the cube, each of these terms must
reduce to a constant:

}2 d2
1 (x) = E1 (8)
2m 1 (x) dx2
}2 d2
2 (y) = E2
2m 2 (y) dy 2
}2 d2
3 (z) = E3
2m 3 (z) dz 2

The stationary states for a particle con…ned to a cube are obtained from these three separate equations.
The energies E1 , E2 , and E3 are separation constants and represent the energy of motion along the three
Cartesian axes x, y, and z. Consistent with this identi…cation, the Schrödinger equation requires that E1
+E2 +E3 = E. q
Independent solutions to this equation are "sin k1 x" and "cos k1 x", where k1 = 2mE
}2
1
is the wavenumber
of oscillation. However, sin k1 x satis…es the condition that the wavefunction must vanish at the wall x=0,
Requiring the wavefunction to vanish also at the opposite wall x = L implies
n1
k1 L = n1 ; n1 = 1; 2; 3; ::: =) k1 =
L
It follows that the magnitude of particle momentum along this direction must be one of the special values
of
} h
jpx j = }k1 =)= n1 ; for,} =
L 2
Similarly

}
jpy j = }k2 =)= n2 ;
L
}
jpz j = }k3 =)= n3
L
Note: n1 = n2 = n3 6= 0: The value of zero mean is zero everywhere in the box, which is not allowed.
And the total energy is de…ned as
1 1 } } }
E= jpx j2 + jpy j2 + jpz j2 = jn1 j2 + jn1 j2 + jn1 j2
2m 2m L L L

1 2 }2 2 2 2 1 h2
E= n 1 + n 2 + n 3 = n1 2 + n2 2 + n3 2 (9)
2m L2 8m L2
 Hence the stationary states solution becomes,
i!t
(x; y; z; t) = A sin(k1 x) sin(k2 y) sin(k3 z)e ; for 0<(x,y,z)<L
3=2
2
(x; y; z; t) = 0; otherwise, Here A=
L
Hence three quantum numbers are needed to specify the quantum condition, corresponding
to the three independent
R1 degrees
R 1 of freedom for a particle in space.
2 2
Note:Evaluate 0 e-ax dx and -1 e-ax dx
Let the integral may be taken along x-axis, or y-axis without a¤ecting its value
Z 1 Z 1
-ax2 2
I= e dx = e-ay dy
0 0
Hence the square becomes as double integral
Z 1 Z 1
2 2
I2 = e-ax dx: e-ay dy
0 0
Z 1Z 1
2 +y 2
I2 = e-a(x ) dxdy = It is 1st quadrant of xy-plane
0 0
So the double integral is calculated by trnasforming to polar coordinates in which,

x2 + y 2 = r2
and di¤erential element of area is

dA = rd dr; r : 0 ! 1; : 0 ! =2

Henceforth,
Z 1Z 1 Z 1Z =2
-a(x2 +y 2 ) 2
I = 2
e dxdy = e-ar rd dr
0 0 0 0
Z 1 Z =2 Z 1 h i Z 1
2 2 =2 2
I2 = e-ar rdr d = e-ar rdr j0 = e-ar rdr
0 0 0 2 0
Z 1 Z =2 Z 1 h i Z 1
2 2 =2 2
I2 = e-ar rdr d = e-ar rdr j0 = e-ar rdr
0 0 0 2 0
Z 1 Z 1
2 2a 1 2
I2 = e-ar rdr = e-ar ( 2ar) dr
2 0 2a 2 2a 0 | {z }
Z Z
1 1
d -ar2 1 2
1
1 h -ar2 i1
I 2 == e dr = de-ar = e
2 2a 0 dr 2 2a 0 2 2a 0
h
1 -ar2 i 1 1
I2 = e = [ 1] =
2 2a 0 2 2a 4a
r r
1
I= =
4a 2 a

Translational Partition Function(of monoatomic or nobel or unreactive gases):

Consider a molecule con…ned to a cubic box(3D). A molecule inside a cubic box of length L has the
h2 2 2 2
translational energy levels given by E = 8mL 2 (nx + ny + nz ); where nx , ny and nz are the quantum numbers

in the three directions. So Translational partition function becomes, Taking = kB1T

X 1
X h2 n2
1
X h2 n2 1
X h2 n2
i h2 y
(n2x +n2y +n2z ) x z
Ztr = qtr = e kB T
=e 8mL2 = e 8mL2 e 8mL2 e 8mL2

i nx =1 ny =1 nz =1
 1
X h2 n2
1
X h2 n2 1
X h2 n2
x y z
qtr = e 8mL2 e 8mL2 e 8mL2 = qtx qty qtz
nx =1 ny =1 nz =1
R1 an2 dn
p h
For very closely spaced levels, we can replace each sum into integral,[ 1 e = 4a ], B = p
2 kB T m

h2 2
n
Z 2 x s r r
1
X h2 n2
x
1 |8mL
{z } 2 kB T mL2 2 kB T m
qtx = e 8mL2 = e a dn = h2
= = L
1 4 8mL h2 h2
nx =1 2

r
2 kB T m L L
qtx = L= =
h2 p h
B
2 kB T m
3=2
L L L L3 V 2 kB T m
qtr = qtx qty qtz = : = 3 = 3 = V
B B B B B h
p 3=2
2 mkB T
qtr = V
h
Example:Find translational partition function of an I2 ;molecule at 300k, Assume V=1liter=10 3 m3
Sol-Example:2 kB T m = 2 3:14 2 127amu 1:6606 10 27 kg=amu 1:3807 10 23 J=K 300K =
| {z } | {z } | {z }
1:0969 10 44 Jkg
3=2
2 mkB T
qtr = V
h
3=2
1:0969 10 44 Jkg
qtr = 10-3 m3 = 3:95 1030
6:6262 10 34 Js
3:95 1030 quantum states are thermally accessible to the molecular system.
Example: Calculate the translational partition function for an O2 molecule in a 1 L vessel at 250 C.
Sol-Example:2 kB T m = 2 3:14 2 32amu 1:6606 10 27 kg=amu 1:3807 10 23 J=K 298K
| {z } | {z } | {z }
3=2
2 mkB T
qtr = V = 1:77 1029
h

How To Find Rotational Energy and Partition Function:

To …nd Rotational Energy, Let Starting from Translational K.E,
1 1
K:ET rans = m
|{z} v 2 ,we can infere fom here, that, K:Erot = I !2
2 2 |{z}
Trans. inertia rot.inertia
The classical energy of a freely rotating molecule can be expressed as rotational kinetic energy
 1 1 1
Erot = Ix ! 2x + Iy ! 2y + Iz ! 2z
2 2 2
where x, y, and z are the principal axes of rotation and Ix represents the moment of inertia about the
x-axis.
In terms of the angular momenta about the principal axes, the expression becomes

L2x L2y L2 L2
Erot = + + z =
2Ix 2Iy 2Iz 2I

I! 2 L2
Erot = = ; "for axially symmetric body"
2
|{z} 2I
|{z}
rot.energy in inertia and ang.freq = rot.energy in terms of angular momentum and inertial

Momentum Operator notation: In quantum mechanics, we operate an operator on the wave function
i) Linear momentum: This operator provides a linear momentum,

~ @
px = mvx =) px(op) = i~rx =
i @x
ii) Angular momentum gives,

d ~ @
Lz = Iz ! z = Iz ; = (angle) =) Lz(op) =
dt i@
Rotational Energy and its operator:

I! 2 L2 J2 L2op ~2 @ 2
Erot = = = =) H(op) = =
2 2I 2I 2I 2I @ 2
m1 m2 2
I= r =) I = r2
m1 + m2
| {z }
reduced mass

"lighter the reduced mass the greater the frequency"

Hamiltonian for rotating molecule:The formation of the Hamiltonian for a freely rotating molecule,
simply replace the angular momenta with the corresponding quantum mechanical operators. The simplest
molecule is "diatomic".For a diatomic molecule the rotational energy is obtained from the Schrodinger
equation with the Hamiltonian expressed in terms of the angular momentum operator as follows,

L2op
H(op) = = EJ
2I |{z}
eigen energy

J (J + 1) ~2 J (J + 1) h2
Erot = =
| 2I {z 8 2I }
rot.energy is quantized

where J(rotational quantum number) is a positive integer.(When a particle loses angular momentum, it
is said to have transitioned to a lower rotational energy state correspond to discrete rotational energy states.
)
Generally, we de…ne a rotational constant B for the molecule

~2 h2
B= = 2 ; = rotational constant
2I 8 I
so that the solutions for the energy states of a rigid rotator can be expressed as

EJ = J (J + 1) B; (J = 0; 1; 2:::) = rotational energy levels,

 In practice, what is measured experimentally is not energy but frequency, or wavenumber. Therefore,
we convert the
energy levels having dimensions of either frequency, by dividing by h, giving

Erot J (J + 1) h
= = = J (J + 1) B
h 8 2I
or wavenumber, by dividing by hc,

Erot J (J + 1) h
k= =
hc 8 2 Ic
For the quantum number L there is ml , -l ml l, and the energy doesn’t depend on ml . Thus the lth
energy level occurs (2l + 1) times in the partition function,
So rotational Partition function

X l
1 X 1
X 1
X
Erot l(l+1)~2 l(l+1)~2
zrot = e kT = (2l + 1) e 2IkT = (2l + 1) e 2I
| {z }
l=0 ml = l l=0 l=0
degeneracy=g l

Note:L2op = ~2 l (l + 1) ; J = l + s:The term 2l + 1 is called a degeneracy factor.

Vibrational energy and Partition function of a diatomic molecule:
Monoatomic molecules or single molecule does NOT show vibrational motion. In molecules, covalent
bonds vibrate at only certain allowable frequencies
Vibrational Modes:Nonlinear molecule with (n) atoms have 3 translational, 3 rotational, so the vibra-
tional modes are (3n-6), as sum of translational, rotational, vibrational are (3n) modes
Example:For H2 O, n=3 atoms, degree of freedom=3n=9, number of vib modes=3n-6=3,
Similarly Linear molecule with (n) atoms cannot rotate about bond axis, i.e., 3 translational, 2 rotationals
has (3n - 5) vibrational modes
Example:For C2 O, n=3 atoms, degree of freedom=3n=9, number of modes=3n-5=4

The (vibrational) energy levels of a quantum harmonic oscillator of frequency ! are

1
En = (n + )~!
2
 1
X 1
X (n+ 1
Evib 2 )~!
zvib = gv e kT = e kT ; n = 0; 1; 2; 3; :::; gv = 1
n=0 n=0
2 3
1 ~! 1
X 1 ~!
2 (n)~! 2 ~! 2~!
zvib = e e =e 4e0 + e + + :::}5
{ze
kT kT kT kT kT
|
n=0 Taylor
2 3 1 ~!
2 1
1 ~!
2 ~!
41 + e
~! 2~! e kT e 2
zvib = e kT
|
kT +
{ze
kT + :::}5 = ~! = ~!
1 e kT 1 e
Taylor expansion

Importance of Partition Function:

A partition function is the bridge between thermodynamics, spectroscopy, and quantum mechanics.
Once it is known, a partition function can be used to calculate thermodynamic functions, heat capacities,
entropies, and equilibrium constants.
All thermodynamics(properties) of a system can be obtained if we know (microstates) or Z(partition
function). Finding Z is much easier than …nding .
Thus Statistical Mechanics heavily depends on PARTITION FUNCTION. Thus Partition Function
has a central role in statistical thermodynamics because once it is known as a function of the variables
on which it depends, all thermodynamic quantities may be calculated from it directly. We use partition
function through ENSEMBLE Theory.