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Diatomic Molecule Partition Function
Diatomic Molecule Partition Function
Diatomic Molecule Partition Function
pi = exp(-i) / q
where pi is the probability of a molecule being found in a state i
with energy i. q is called the molecular partition function,
q = i exp(-i)
The summation is over all possible states (not the energy
levels).
Independent Molecules
Consider a system which is composed of N identical molecules.
We may generalize the molecular partition function q to the
partition function of the system Q
Q = i exp(-Ei)
where Ei is the energy of a state i of the system, and summation
is over all the states. Ei can be expressed as assuming there is
no interaction among molecules,
En = n2h2 / (8mX2) n = 1, 2,
Setting the lowest energy to zero, the relative energies can then
be expressed as,
n = (n2-1)
= h2 / (8mX2)
with
qx = n exp [ -(n2-1) ]
qT = q x q y q z
= (2m/h22)1/2 X (2m/h22)1/2 Y (2m/h22)1/2 Z
= (2m/h22)3/2 XYZ = (2m/h22)3/2 V
= V/3
Heat Capacity
Cv = (E/T)V = 3/2 nR
Diatomic Gas
Consider a diatomic gas with N identical molecules. A molecule is made
of two atoms A and B. A and B may be the same or different. When A
and B are he same, the molecule is a homonuclear diatomic molecule;
when A and B are different, the molecule is a heteronuclear diatomic
molecule. The mass of a diatomic molecule is M. These molecules are
indistinguishable. Thus, the partition function of the gas Q may be
expressed in terms of the molecular partition function q,
Q q N / N!
q i exp( i )
where, i is the energy of a molecular state I, =1/kT, and is the
summation over all the molecular states.
exp( ) exp[ ( )]
[ exp( )][ exp( )][ exp( )][ exp(
T
i
q T q R qV q E
T
i
R
i
R
i
V
i
V
i
E
i
E
i
)]
q T V / 3
w / qE 1
where
h( / 2M )1/ 2
1 / kT
kT
hv
q v 1 e e 2 e 3 ...
e q v e e 2 e 3 .... q v 1
Therefore,
1
q 1 /(1 e
)
1 e hv
Consider the high temperature situation where kT >>hv, i.e.,
Vibrational temperature v
k v hv
High temperature means that T>>v
e hv 1 h
F2
HCl H2
v/K 309 1280 4300 6330
v/cm-1 215 892 2990 4400
where
k
m
hv 1, q v 1 / hv kT / hv
h/8cI2
hcB<<1
c: speed of light
I: moment of Inertia
I mi r i2
i
=kT/hcB
Note: kT>>hcB
q R kT / 2hcB
Generally, the rotational contribution to the molecular partition function,
q R kT / hcB
Where is the symmetry number.
H 2O NH 3 CH 4
2
3 12
Rotational temperature R
k R hcB
qV = kT/hv
qR = kT/hcB
The rule: at high temperature, the
contribution of one degree of freedom
to the kinetic energy of a molecule
(1/2)kT
Partition Function
q = i exp(- i) = j gjexp(- j)
Q = i exp(-Ei)
qq q q q
T