Molecular Thermodynamics (CH3141)

The ideal gas II: Intramolecular degrees of freedom

Sandler Ch4

Molecular rotations
Molecular vibrations
Equipartition of energy

N.A.M. (Klaas) Besseling

1

Summary of what we learned about the ideal gas so far:

The total partition function Q of an ideal gas can be build
up from single-molecule partition functions q:

E
Q = exp i
kT
i
Divide and Rule! (independent modes or atoms)
For a one-component ideal gas (Maxwell-Boltzmann statistics)
1 N
Q=
q
N is the number of molecules
N!

with q = exp n
kT
n

division by N! because of the indistinguishability of the N

atoms of the same kind.
2

Divide and rule further!

Translational and internal degrees of freedom are independent
hence, the single-molecule partition function can be factorised:

q = qtrans qint

For the mono-atomic ideal gas at not-too-high T,

- qint is trivial and only qtrans matters,
- we can write:

q = qtrans
(taking the electronic and nuclear partition functions equal to 1)
3

. . . and further (independent translational modes)

There are 3 independent translational degrees of freedom,
hence ztrans itself can be factorised:

qtrans = qx qy qz with qx = exp lx
etc.
kT
lx

where lx =

2 2
x
2
x

hl
are the energy levels of a particle in a 1D box
8mL

Because the energy levels are closely spaced ( << kT ) ,

and vary smoothly with lx, the sum can be replaced by an
integral, solving the integral yields

qx =

Lx

where =

h
2 mkT

thermal wavelength
4

We can use this to construct the total partition function:

for the monoatomic ideal gas

Q=

1 N
1 VN
q =
N!
N ! 3N

which directly yields an expression for the Helmholtz energy

because
A = kT lnQ
Hence expressions for all desired thermodynamic properties
can be obtained:
e.g.
pressure (ideal gas law)
energy ( 21 kT per degree of freedom)
heat capacity
entropy
5

Intramolecular degrees of freedom

So far we discussed the monoatomic ideal gas at not-too-high T ,
for which only translational degrees of freedom are relevant.
Then the single-molecule partition function essentially equals the
translational partition function:

l
q = qtrans = exp trans
kT
ltrans

Often intramolecular degrees of freedom are relevant:

Internal and translational degrees of freedom are independent;
! Energies are additive

l + iint

q = exp i = exp trans

kT ltrans iint
kT

i
Hence, we can write the single-molecule partition function as a product

q = qtrans qint

with

l
qtrans = exp trans
kT
ltrans

i
qint = exp int
kT
iint

check this; show that indeed

ltrans + iint
ltrans
iint
exp

=
exp

exp
kT l kT
kT

ltrans iint
iint
trans

Internal molecular degrees of freedom

Sandler 4.1

The internal molecular state is a combination of:

the rotational, vibrational, electronic, and nuclear states

q = qtrans qint

qint qrot qvib qele qnuc

this presumes that

rotational, vibrational, electronic, and nuclear states are independent
!!! This is only approximately true under certain conditions !!!
(details later)

Q=

1 N
1
q =
( qtrans qint )N
N!
N!

A = kT lnQ = kTN ( ln N ln qtrans ln qint 1) check this

N 3

= kTN ln
ln qint

eV

check this

ln qint ln qrot + ln qvib + ln qele + ln qnuc

8

 N 3

A = kTN ln
ln qint

eV

what modification to the expression for chemical potential

that we have seen so far: = kT ln 3

arise from the intramolecular degrees of freedom?

Term of Helmholtz energy: kTN ln qint

N
with intramolecular
degrees of freedom:

V ,T

qint independent of N

kT ln qint

3
= kT ln ( 3 ) ln qint = kT ln
qint

Nuclear and electronic states

Often ok to assume that only
ground states (states with lowest energy levels) are relevant.
(ok at moderate temperatures, then >> kT )
There may be more than one state with the same energy level.
the nr. of states with same energy is called
the degeneracy or multiplicity of that energy level

Then qel = exp el,j el,1 exp el,1 = el,1
j=1
kT
kT

choosing the ground state level

to be the zero of energy

10

1 enters q just as a constant factor.

Hence it enters the Helmholtz energy only as
a constant contribution per molecule:
Irrelevant for measurable thermodynamic properties
(if no chemical reactions occur!)
So it is often taken to be just 1 (even if it is not).
Then terms lnqel,1 in the free energy are simply omitted

(lnq

el,1

= ln1 = 0

Similar arguments apply to nuclear states.

hence:

qint qrot qvib qele qnuc qrot qvib

11

Vibrational and rotational states

Polyatomic molecules have vibrational and rotational degrees
of freedom.
It is a reasonable approximation to assume that vibrational and
rotational degrees of freedom are independent:

qint qvib qrot

This is not completely exact; it neglects centrifugal effects

12

Sandler 4.1c

Molecular vibrations
If vibration energies not too high,
molecular vibrations can be approximated as
harmonic oscillation (oscillations in a parabolic potential energy),
and as
separable in independent vibrational normal modes.
Hence

qvib qvib1 qvib2 qvib3 . . .

The number of modes depends on the molecular structure.

13

A diatomic molecule
has only one vibration
mode

vibration modes of the CO2 molecule

(linear tri-atomic molecule ! three modes)

more complex
molecules ! more
vibrational modes
In the following we
focus on just one mode,
indicated by subscript vib
without a number.
14
diagram by Derek Kverno at http://www.cartage.org.lb/en/themes/sciences/Physics/MolecularPhysics/MolecularSpectra/MolecularSpectroscopy/MolecularSpectroscopy.htm

Harmonic potential (= parabolic potential):

dV
(Hookes law)
V (x) = 12 Kx 2 F(x) =
= Kx
dx
x = displacement of oscillator from its minimum-energy state
K = spring constant
V = potential energy
F = restoring force
We have chosen V (0) = 0
For mass m in a parabolic potential
1
the vibration frequency is =
2

K
m

from Classical Mechanics: Christiaan Huygens 1673

Horologium oscillatorium sive de motu pendulorum

more generally:
m to be replaced by a reduced mass
e.g. diatomic molecule: m1m2 ( m1 + m2 )

15

j=6

the energy levels are

vib, j = ( j + 12 ) h
(j = 0, 1, 2, . . . )

choosing the minimum

potential as the zero of energy:
ground state energy: 0 = 12 h

j =5
j=4
j=3
j=2
j =1
j=0

(from http://131.104.156.23/Lectures/CHEM_207/vibrational_spectroscopy)

According to the
Schrdinger equation for
a harmonic potential energy well

equidistant energy levels: vib = h

The temperature for which vib = kT is vib = h k

O(1000K )
16

With the Boltzmann distribution law in mind,

we understand immediately, without any further calculations,
that
If kT << = h that is if T < vib = h k
then only the ground state is occupied,
the higher energy states are virtually unoccupied.
(this is the low-T limit)
This is usually approximately true at room temperature since

vib O (1000K )
17

The partition function for one vibrational mode is

j + 1 h
exp
kT2
j=0

h
jh
= exp
exp
2kT
kT
j=0

qvib = exp j =
j=0
kT

using

i=0

h
h
= exp
exp

2kT j=0
kT

x i = 1 (1 x ) (geometric series)

vibrational temperature vib

qvib

h
k

exp ( 12 vib T )
exp ( 12 h kT )
=
=
1 exp ( h kT ) 1 exp ( vib T )
18

Low temperature limit

T << vib h k (energy-level spacing vib = h >> kT )
then ~ only the ground state occupied:

qvib =

exp ( 12 h kT )
1 exp ( h kT )

h

qvib exp
= exp vib

2kT
2T
(just the first term of partition func.)

Contributions per molecule to the:

Helmholtz energy: avib = kT ln qvib = 12 h
energy:

vib = k

entropy:

(mean energy of vibrational mode)

heat capacity:

d avib T

= 12 h
d1 T
svib = vib avib T = 0
d
cvib = vib = 0
dT

19

High temperature limit

energy-level spacing kT >> h : classical limit

qvib =

exp ( 12 h kT )
1 exp ( h kT )

qvib

with exp x 1+ x for |x|<<1

kT
T
=
h vib

check this

qvib =

exp

( x ) 1+
1
2

1 exp x

1
2

1
x

Contributions per molecule to the

kT
h
da T
d ln1 T
1
energy: vib = k vib = k
=k
= kT
d1 T
d1 T
1T

Helmholtz energy: avib = kT ln qvib = kT ln

heat capacity:

cvib =

d vib
=k
dT

20

?
10

Graphical summary
of dependence of
vib and cvib on T

vib =

h
+
e
1 2
it
lt
im
u
l
s
e
T
hct r
a
g
i
x
e
h
h kT

low-T limit:
just the
ground-state energy

vib
high-T limit: k

Cvib
low-T limit: 0

NB:
vib O(1000K)

vib

Molecular rotations

21

Sandler 4.1b

Assuming that vibrations and rotations are independent:

qint = qvib qrot

implies that rotations are treated as if molecules are rigid rotors
(neglecting centrifugal effects)

- mono-atomic molecules: 0 rotational modes

- linear molecules:
2 rotational modes
- non-linear molecules:
3 rotational modes

22

11

Hetero-nucleic diatomic molecule (e.g. CO)

mA

R
mB

reduced mass
m m
= A B
mA + mB

rotation of di-atom AB with AB distance = R

equivalent with
movement of a mass on the surface of a sphere with radius R
Hence in the classical limit the partition function
is the same as that for translational movement
of a particle with mass in a 2D box of area 4R 2 :

So we can use expression ~ translational motion

2 kT
qrot =
h 2

22

4 R 2

= translational single-particle partition function

of a particle with mass in a 2D box of size 4R 2
in the classical limit (check this)

qrot =

8 2 IkT
T
=
2
h
rot

I = R 2 = moment of inertia
h2
rot = 2
= rotational temperature
8 Ik
24

12

If the classical limit does not apply

(low T, kT or smaller)
the actual values of the lowest energy levels are important.
These do not just depend on the size, but also on the shape
of a 2D box.
Then the correct rotational energy levels have to be used.
Makes things more complicated (see Sandler)

25

Molecular symmetry
Homo-nuclear diatomic molecule (e.g. N2)
The two nuclei are indistinguishable
Rotational partition function as given above
needs to be devided by 2:
Generally:

qrot =

8 2 IkT
T
=
2
h
r

where the symmetry number

1
=
2

heteronuclear
homonuclear

each orientation of a homonuclear = symmetric linear molecule

corresponds to
two orientations of a heteronuclear = asymmetric linear molecule
26

13

The contribution to the Helmoltz energy per molecule is

arot = kT ln qrot

with

qrot =

8 2 IkT
h2

The contribution to the energy per molecule is

rot =

d arot T
d1 T

=k

dln1 T
= kT
d1 T

That is 21 kT per degree of freedom

(a diatomic molecule has two rotational degrees of freedom)
For non-linear molecules: rot = 23 kT
The contribution to the heat capacity per molecule is crot =

d rot
dT
27

Overview for molecular systems at room temperature:

translations

<< kT (classical limit applies)

rotations

<< kT (classical limit applies)

vibrations

kT

(classical limit may be used )

molecular electronic

>> kT (only ground state relevant)

nuclear

>> kT (only ground state relevant)

increasing
energy spacing

28

14

The Equipartition Theorem

The Law of Equipartition of Energies
Equipartition = division in equal parts
each degree of freedom contributes an equal amount

1
2

kT to energy

In the classical limit (high temperatures),

for translations and rotations and vibrations
the mean energy per molecule, per degree of freedom is always

1
2

kT

For vibrations it is kT per molecule for each normal mode.

This is in the classical limit
1
kT for potential energy and
2
1
kT
for kinetic energy.
2

29

Why so often this 21 kT ?

Because of the quadratic expressions for the energy:
if the energy for a degree of freedom of a particle can be written
as Cy2
where C is some constant coefficient
y defines the state for a degree of freedom
y can be,
- in classical mechanical terms: a (angular) velocity
component. Then Cy2 is a kinetic energy.
- a position coordinate in the case of a harmonic potential.
Then Cy2 is a potential energy.
- in quantum mechanical terms: a quantum number, e.g. as for
translation (check e.g. in previous handouts)
30

15

for each translational degree of freedom,

in classical mechanical terms: 21 mv x2
(in quantum mechanical terms this is lx2 )
for each rotational degree of freedom,
in classical mechanical terms: 21 I 2
I = moment of inertia, = angular velocity
2
for vibrational modes, kinetic energy: 12 mv x
+ potential energy; if vibration is harmonic: 21 kx 2

31

y defines microstate of some mode

2
if energy of the state can be written as y = Cy

the partition function

Cy 2
kT
q = exp
dy =
classical expression

C
kT

y (treated as) continuous

the corresponding Helmholtz energy contribution

k

kT
a = kT ln q = kT ln
= 12 kT ln
+ lnT
C
C

with the Gibbs-Helmholtz relation:

d a T 1 d ln1 T 1
=
= k
= 2 kT
d1 T 2 d1 T
This result does not depend on C,
only on the quadratic character of y = Cy 2
32

16

Give a rough estimate of the heat capacity of a mole of CO

based on the equipartition theorem
at ~ room temperature (assuming low-T limit can be used for vibr)
at ~ 5000 K (assuming that it does not decompose)
room temperature
translations
<< kT (classical limit applies)
3 21 R
rotations
vibrations

<< kT (classical limit applies)

2 21 R

> kT (low-T limit)

0
5 21 R

5000 K
translations

<< kT (classical limit applies)

3 21 R

rotations

<< kT (classical limit applies)

2 21 R

vibrations

> kT (classical limit applies)

2 12 R
7 12 R

33

Constant-volume Molar Heat Capacities

of some gases at 15 oC, 1 atmosphere
gas

CV

J
mole.K

CV
R

Ar

12.5

1.50

He

12.5

1.50

CO

20.7

2.49

HCl

21.4

2.57

N2

20.6

2.49

NO

20.9

2.51

CO2

28.2

3.40

34

17