Energy Levels

Energy Levels
To predict the properties of materials from the forces on the atoms
that comprise them, you need to know the energy ladders
Energy ladders can be derived from spectroscopy or quantum
mechanics
Energy Levels
Spectroscopy
Spectroscopy measures the
frequency v of
electromagnetic radiation
that is absorbed by an atom,
a molecule, or a material
Adsorption of radiation by
matter leads to an increase
in its energy by an amount


This change is the difference
from one energy level to
another on an energy ladder
h c v A =
Rotational (l) and vibrational
(v) energy levels for HBr
Energy Levels
Quantum Mechanics
The basis for predicting quantum mechanical energy levels is the
Schrdinger equation


The wavefunction (x,y,z) is a function of spatial position
The square of this function,
2
, is the spatial probability
distribution of the particles for the problem of interest
The Hamiltonian operator H describes the forces relevant for the
problem of interest
In classical mechanics the Hamiltonian is given by the sum of
kinetic and potential V energies
For example, for the one-dimensional translational motion of a
particle having mass m and momentum p
j
E = H
( )
2
2
p
x
m
= + H V
Energy Levels
Quantum Mechanics
While classical mechanics regards p and V as functions of time
and spatial position, quantum mechanics regards p and V as
mathematical operators that create the right differential equation
for the problem at hand
In one dimension, the translational momentum operator is



Schrdingers equation is now



Only certain functions (x) satisfy this equation
The quantities E
j
are called eigenvalues and represent the discrete
energy levels that we seek
The index j for the eigenvalues is called the quantum number
2 2
2
2 2
4
h d
p
dx t
| |
=
|
\ .
( )
( ) ( ) ( )
2
2
2 2
8
j
d x
h
x x E x
m dx

t
| |
+ =
|
\ .
V
Translational Motion
The Particle-in-a-Box Model
The particle-in-a-box is a model for the freedom
of a particle to move within a confined space
A particle is free to move along the x-axis over
the range 0 < x < L
At the walls (x = 0 and x = L) the potential is
infinite (V(0) = V(L) = )
Inside the box the molecule has free motion
(V(x) = 0 for 0 < x < L)
Schrdingers equation is




The solution to this differential equation is
2
2
2
0
d
K
dx

+ =
2
2
2
8 m
K
h
c
= with
( ) ( ) ( )
sin cos x A Kx B Kx = +
Translational Motion
The Particle-in-a-Box Model
The boundary conditions are



Applying the boundary conditions and
normalizing the probability distribution
gives the following expressions for the
wavefunction
n
and energy c
n
for a
given quantum number n
( )
0 0 = ( )
0 L =
and
( )
1 2
2
sin
n
n x
x
L L
t

| | | |
=
| |
\ . \ .
2 2
2
1, 2, 3,
8
n
n h
n
mL
c = =
Translational Motion
The Particle-in-a-Box Model
Here are the wavefunctions and probabilities for select values of n
Example: Energy Levels for Argon
What are the energy levels for an argon
atom contained in a one-dimensional box
of length L = 1 cm?
Translational Motion
Translational Partition Function
Now that we have the energy ladder, we can compute the
translational partition function q
trans




To access the relative population of an energy level we introduce
the translational temperature u
trans




The Boltzmann factors in the above expression are now
Since u
trans
is very small compared to typical temperatures (based on
the previous example, u
trans
~ 6 10
16
K), numerous energy levels
will be populated at typical temperatures of interest
As a result, the summation over n can be replaced by an integral
( )
2 2 2
8
trans
1 1
n
n h mL kT
kT
n n
q e e
c

= =
= =

2
trans
2
8
h
mL k
u =
2
trans
n T
e
u
Translational Motion
Translational Partition Function
We now have




Evaluation of this integral gives
( )
2 2 2
8
trans
0
n h mL kT
q e dn

=
}
1 2
trans
2
2 mkT
q L
h
t
| |
=
|
\ .
Translational Motion
Three-Dimensional Box
Now suppose that a particle is confined within
a three-dimensional box with dimensions
0 < x < a, 0 < y < b, and 0 < z < c
In this case, it turns out that Schrdingers
equation can be separated to obtain the
following solution
( ) ( ) ( ) ( )
, , x y z x y z =
2
2 2 2
, ,
2 2 2
8
x y z
y
x z
n n n
n
n h n
m a b c
c
| |
= + +
|
\ .
, , 1, 2, 3,
x y z
n n n =
Translational Motion
Three-Dimensional Partition Function
The three-dimensional translational partition function is given by







Where V is the volume of the box and A is the de Broglie
wavelength
3 2
trans
2
2
x y z
mkT
q q q q abc
h
t
| |
= =
|
\ .
trans
3
V
q =
A
3 2
2
3
2
h
mkT t
| |
A =
|
\ .
Example: Translational Partition Function for Argon
Calculate the translational partition function
for argon at T = 273 K and standard state
volume V = 2.24 10
2
m
3
Vibrational Motion
Harmonic Oscillator Model
We treat vibrational motion with a harmonic
oscillator model
The potential energy is given by



Schrdingers equation is



Solution of the above differential equation leads to the following
energy levels
( )
2
1
2
s
x k x = V
( )
( ) ( )
2
2
2
2 2
1
8 2
s v
d x
h
k x x x
m dx

c
t
| |
+ =
|
\ .
1
0,1, 2,
2
v
v h v c v
| |
= + =
|
\ .
1 2
1
2
s
k
m
v
t
| | | |
=
| |
\ .\ .
with
Vibrational Motion
Vibrational Motion
Diatomic molecules
To extend the harmonic oscillator model to diatomic molecules we
have to slightly alter the vibrational frequency v by introducing the
reduced mass
1 2
1
2
s
k
v
t
| |
| |
=
|
|
\ .
\ .
1 2
1 2
m m
m m
=
+
Vibrational Motion
Vibrational Partition Function
The vibrational partition function is now




This summation has a closed-form solution



This expression is often written as
1
2
vib
0 0
v
v h kT
kT
v v
q e e
v
c
| |

+
|

\ .
= =
= =

2
vib
1
h kT
h kT
e
q
e
v
v

vib
vib
2
vib
1
T
T
e
q
e
u
u

vib
h
k
v
u =
with
Example: Vibrational Partition Function for Oxygen
Diatomic oxygen molecules have a
vibrational frequency of 1580 cm
l
. Calculate
the vibrational partition function for oxygen
at 300 and 1000 K.

Rotational Motion
Rigid Rotor Model
The rotational motion of a molecule is
treated using a rigid rotor approximation
Classically, a mass m orbiting at a distance
R around a center point with a tangential
velocity v
t
, has the following angular
momentum L and kinetic energy K
2
1
2
t
t
L mRv
K mv
=
=
Here, we are interested in a related problem we examine the
rotational motion of two masses m
1
and m
2
separated by a rigid
connector of length R
Rotational Motion
Rigid Rotor Model
Applying the Hamiltonian operator for the motion described by
u and | gives the following for Schrdingers equation




Where is the reduced mass and I = R
2
is the moment of inertia
The solutions to the above expression is given in terms of spherical
harmonic functions
The following energy levels c
l
with degeneracies g
l
result
( )
2 2
2 2 2 2
1 1
, sin
8 sin sin
h
R
u | u c
t u u u u |
( c c c
| |
= + =
|
(
c c c
\ .

H
( )
2
2
1
8
l
l l h
I
c
t
+
=
2 1
l
g l = + and
0,1, 2, l =
Rotational Motion
Rigid Rotor Model
The partition function is now given by



We now define the rotation temperature u
rot
as



For T >> u
rot
, the summation above can be approximated by an
integral with the following result



Where o is a nuclear and rotation symmetry factor that accounts for
the number of equivalent orientations of a molecule
2
rot
2
8
h
kI
u
t
=
( )
rot
0
2 1
l
kT
l
q l e
c

=
= +

2
rot
2
rot
8 T IkT
q
h
t
ou o
= =
Rotational Motion
Symmetry Number
Here are the symmetry numbers for a number of common molecules
Molecule Formula o
Hydrogen Chloride HCl 1
Nitrogen N
2
2
Carbonyl Sulfide COS 1
Carbon Dioxide CO
2
2
Water H
2
O 2
Ammonia NH
3
3
Methane CH
4
12
Benzene C
6
H
6
12
Rotational Motion
Rigid Rotor Model
For nonlinear molecules with three principal moments of inertia
I
a
, I
b
, and I
c
, the rotational partition function is





( )
3 2
1 2
2
rot
2
8
a b c
I I I
kT
q
h
t
t
o
| |
=
|
\ .
Example: Rotational Partition Function for Oxygen
The length of a bond in an oxygen molecule
is R = 1.2074 , and the mass of each atom is
m = 16 g/mol. Determine the rotational
partition function at T = 300 K.

Electronic Partition Function
The Electronic Partition Function
The partition function that accounts for the various states of
electronic excitations is


Where the g
i
s are the electronic degeneracies and the Ac
i
s are the
electronic excited state energies
Typically the Ac
i
s are rather large and only the ground state is
significantly populated at ambient temperature, q
elec
g
0

Here are the first few electronic states for H and O

1 2
elec 0 1 2
kT kT
q g g e g e
c c A A
= + + +
Ideal Gas Properties
The Total Partition Function
We now wish to calculate thermodynamic properties for ideal gases
from the partition function
The total partition function is



To obtain thermodynamics properties we apply the expressions
developed in Chapter 10 that link thermodynamic properties to the
molecular partition function

tot trans rot vib elec
q q q q q =
Ideal Gas Properties
Ideal Gas Pressure
To obtain the pressure we use the relationship



Since only the translation partition function is dependent upon
volume

,
ln
T N
F q
p NkT
V V
c c
| | | |
= =
| |
c c
\ . \ .
( )
3
trans
ln
ln ln
q
p NkT NkT V
V V
c c
| | | |
= = A
| |
c c
\ . \ .
NkT
p
V
=
Ideal Gas Properties
Ideal Gas Energy
To obtain U we use the relation



All of the partition functions are dependent upon T
Here are the various contributions

2
ln q
U NkT
T
c
| |
=
|
c
\ .
trans
3
2
U NkT =
rot (linear)
U NkT =
rot (nonlinear)
3
2
U NkT =
( )
vib vib
vib
vib
2 exp 1
U Nk
T
u u
u
| |
= +
|

\ .
Ideal Gas Properties
Ideal Gas Entropy
The entropy is given by



It is now important to remember that ideal gas particles are
indistinguishable, and thus the partition function Q is Q = q
N
/N!
Using Stirlings approximation gives




Application to a monatomic gas gives

ln
U
S k Q
T
= +
( )
ln ln ln
!
N
q U U
S k Nk q k N N N
N T T
| |
= + = +
|
\ .
3 2
5 2
2
2
ln
mkT e
S Nk V
h N
t
(
| |
| |
=
| (
|
\ .
\ .

Example: Absolute Entropy of Argon
Evaluate the absolute entropy of argon at
T = 300 K and p = 1 atm.

Ideal Gas Properties
Ideal Gas Free Energy
The bridge equation gives the free energy
ln ln ln
!
N
N
q eq
F kT Q kT kT
N N
| |
= = =
|
\ .
ln
eq
F NkT
N
| |
=
|
\ .
Ideal Gas Chemical Potential
The chemical potential is given by = (F/N)
T,V
ln ln
N q
kT kT kT
eq N

| |
| |
= + =
|
|
\ .
\ .
Example
Plot the probability distribution for observing a N
2

molecule with a rotational quantum number l in the gas
phase at 300 K. Construct a similar plot for finding a N
2

molecule with a vibrational quantum number v for this
same situation. What are the most probable rotational and
vibrational states to find a N
2
molecule in under these
conditions? Repeat the calculations for I
2
.

Parameters for N
2
: u
rot
= 2.88 K, u
vib
= 3374 K
Parameters for I
2
: u
rot
= 0.0537 K, u
vib
= 308 K
Example
The Equipartition Theorem
Multiples of (1/2) kT
We noted previously that the energies of a molecule due to
translational and rotational motion appear in integral multiples of
(1/2) kT
For example,






We now rationalize this finding in terms of an equipartition of
energies
trans
3
2
U NkT =
rot (linear)
U NkT =
rot (nonlinear)
3
2
U NkT =
The Equipartition Theorem
Average Energies
When a form of energy depends on a degree of freedom x, the
average energy <c> of that component is





When quantum effects are unimportant, i.e., a large number of
states are populated, the summation above can be approximated by
an integral
( )
( )
( )
x kT
x
x kT
x
x e
e
c
c
c
c

( )
( )
( )
x kT
x kT
x e dx
e dx
c
c
c
c

=
}
}
The Equipartition Theorem
Square-Law Functions
Now consider energies that follow a square-law function


Where c is a positive constant
This is the case for both translational and rotational energies
We now evaluate the previous integral to obtain the high-
temperature average energy
( )
2
x cx c =
2
2
2 cx kT
cx kT
cx e dx
e dx
c

=
}
}
1
2
kT c =
The Equipartition Theorem
Square-Law Functions
This implies that each degree of freedom contributes (1/2) kT to the
average energy of the system
Also, the average energies depend linearly on temperature
Since constant-volume heat capacities are derivatives of <c> with
respect to T, this result implies that heat capacity values are
constant, with a value of (1/2) k times the number of degrees of
freedom
When more than one type of motion exists (e.g. translation and
rotation), the number of degrees of freedom from each type of
motion are summed to obtain the total average energy
For example, for independent energies A and B, the heat capacity is
given by
( )
, ,
A B
V A B V A V B
C N N C C
T T T
c c
c c
c c
c (
= + = + = +
(
c c c

The Equipartition Theorem
Vibrational Energy
Quantum vibrational energies depend
linearly on the vibrational quantum number


The vibrational equipartition energy is







This result indicates that energy in the amount of kT will partition
equally into each vibrational degree of freedom at high
temperatures
( ) ( )
1
2
v v h c v = +
cx kT
cx kT
cxe dx
e dx
c

=
}
}
kT c =
The Equipartition Theorem
Dependence of the
heat capacity on
temperature for an
ideal gas
Freezing out of
vibrations in
diatomic gases