CHEM 379, Fall 2011 Page 1 of 6

Physical Chemistry Structure Laboratory

Experiment 4: The Absorption Spectrum of Iodine

Background Reading:
In addition to the theory presented below, read the article by R. B. Snadden
1
. For further
details on the theory of electronic-vibrational spectra of diatomic molecules (I
2
in particular),
read the Theory section (pp. 425-428) and the Experimental section (Absorption spectrum,
pp. 428-429) of experiment 40 in Shoemaker 6
th
edition (This experiment is not in the 7
th
or 8
th

editions the relevant text is posted on the course web page). Refer to your Physical Chemistry
textbook for additional background on electronic, vibrational, and rotational spectra of
diatomic molecules.

Total Internal Energy and the Harmonic Oscillator:
A diatomic molecule such as I
2
in the gas phase has an overall internal energy, E
int
.
To a degree of approximation, this energy can be seen as the sum of the energies arising
from the molecules electronic state energy, E
e
, its vibrational state energy, E
v
, and its
rotational state energy, E
r
; i.e.,
E
int
= E
e
+ E
v
+ E
r
(1)
The electronic, vibrational, and rotational energies are individually quantized (Figure 1). The
ground state value of E
int
occurs when all three components are in their ground states
(which arises when the quantum number associated with the type of energy has is lowest
value). However, in a real sample all combinations of allowed values of E
e
, E
v
, and E
r
may
occur for various fractions of the total population of molecules.

Figure 1. Quantized electronic, vibrational, and rotational levels for the internal energy of a
molecule, as Eint =Eelec +Evib + Erot. The quantum numbers v and J are associated with Evib and
Erot, respectively.
CHEM 379, Fall 2011 Page 2 of 6

As shown in Fig 1, the energy separations between the various electronic states are relatively
large, the separations between vibrational states in any electronic state are smaller, and the
separations between various rotational states in any vibrational state are the smallest.
Furthermore, note that the separation between vibrational states gets smaller as the quantum
number v gets bigger, but the separation between rotational states gets larger as the quantum
number J gets larger.
A photon of the appropriate energy could induce a transition between any of these
states. In this experiment we will be looking at the visible spectrum due to transitions from
the electronic ground state to the first electronic excited state; i.e., E
0
E
*
. This transition
can occur from any of the vibrational states in the electronic ground state to any of the
vibrational states in the electronic excited state. Transitions from any of the available
rotational states associated with each vibrational state are also possible, but the energy
differences are too small to result in observable bands at the resolution available on our
spectrophotometers. Thus, we will be looking at bands arising from the combination of
electronic-vibrational transitions.
In either electronic state, the vibrations of the molecule behave approximately like a
harmonic oscillator with energies
E
v
(v+ )e v = 0, 1, 2, ... (2)
where, e=2tv is the vibrational frequency. The energy levels of a harmonic oscillator,
compared to the parabolic energy variation of a classical (non-quantum) oscillator, are shown
in Fig. 2. Note that the lowest energy, at the bottom of the parabolic potential well, is not
possible. At that point, the molecule would be static with its atoms at their equilibrium
internuclear separation. The difference between this energy and the first vibrational state (v
= 0) is the zero-point energy.

Figure 2. The energy levels of a harmonic oscillator

CHEM 379, Fall 2011 Page 3 of 6
The vibrational frequency, e , in any state is the same and is related to the bonds
force constant, k, by the harmonic oscillator expression:

e
k
= (3)
From this it follows:
k = e
2
= 4t
2
=
2
c
2
(4)
where = =e /2t c =v /c is the vibrational frequency in wavenumbers (cm
-1
).
Note that the harmonic oscillator model predicts equal spacing between vibrational
levels. Real molecules have potential energy curves with some degree of anharmonicity,
which causes the spacing between states to decrease as v increases. The potential is often
approximated by a Morse curve, as shown in Fig. 3.

Figure 3. Energy levels of an anharmonic oscillator (Morse potential curve). Note the successively
smaller separations between energy states as v increases (bottom to top).

From the Schrdinger equation for the vibrational levels of a diatomic molecule, the
energy in any state is given by
E
v
= e(v+ ) _e(v+ )
2
+ ... (5)
where _ is the anharmonicity constant. Higher terms in Eq. (5) are usually neglected.
At room temperature, most molecules in a sample of I
2
exist in the electronic ground state.
In that state, most are also in the vibrational ground state (v = 0). However, significant
portions of the population of molecules exist in higher vibrational energy states (v = 1, 2, ...).
Thus, the electronic transition E
0
E
*
may be from any vibrational state v of the ground
electronic state to any vibrational state v of the excited electronic state, as shown in Fig. 4.
Note that the spacing of the vibrational energy levels in the excited electronic state are
different from those in the ground state because of changes in the force constant k (a
CHEM 379, Fall 2011 Page 4 of 6
measure of bond strength).

Figure 4. Electronic-vibrational transitions for the fundamental (left), first hot band (center) and
second hot band (right). The transition notations n,m refer to the vibrational states in the excited and
ground electronic states, respectively.

Following Snadden, we will designate the change in vibrational states with the
electronic transition by the index notation n,m, where n is the value of v' in the electronic
excited state, and m is the value of v in electronic ground state. All transitions from v = 0
(designated n,0) are part of the fundamental band. All transitions from v = 1 (designated
n,1) are part of the first hot band, and all transitions from v = 2 (designated n,2) are part of
the second hot band. In the visible spectrum, instead of a single band for the electronic
transition, we observe three broad bands (the fundamental and two hot bands) with saw-
tooth fine structure corresponding to the various vibrational transitions from a particular
vibrational state v in the electronic ground state to all possible vibrational states v' in the
electronic excited state. The appearance of the band structures can be seen in Snadden's Fig.
2. The fundamental band involves the largest energy separations between states, and so it
occurs at the highest energy (lowest wavelengths) of the three bands.
We will use data from the frequencies (measured as wavelengths) of the vibrational
fine structure of the electronic transitions arising from the fundamental band and the two
hot bands. Within the electronic ground state, we define the energy difference between the
vibrational states v = 0 and v = 1 as X, and the difference between the vibrational states v
=1 and v = 2 as Y, as indicated in Fig. 5.
Thus X = E
0
(v = 1) E
0
(v = 0) and Y = E
0
(v = 2) E
0
(v = 1) (6)
Using the anharmonic vibrational energy given the Morse potential function (Eq. 5),
for X we have
X = E
0
(v=1) - E
0
(v=0) = | e (3/2) _ e (9/4) | | e (1/2) _ e (1/4) |
= e2_ e= e (1 2_ ) = hc= (12_ ) (7)
that, expressed in units of wavenumbers, gives
X = = (12_ ) (8)
CHEM 379, Fall 2011 Page 5 of 6

Figure 5. Pairs of electronic-vibrational transitions that define X as the energy separation between v
= 0 and v = 1 of the electronic ground state, and Y as the energy separation between v = 1 and v = 2
of the electronic ground state.
Similarly, for Y we have
Y= E
0
(v = 2) E
0
(v = 1) = e (5/2) _ e (25/4) | | e (3/2) _ e (9/4) |
= e4_ e= e (1 4_ ) = hc= (14_ ) (9)
that expressed in units of wavenumbers (cm
-1
)
Y = = (1 4_ ) (10)
As can be deduced from Fig. 5, X = v
0,0
v
0,1
= v
1,0
v 1
,1
= v
2,0
v
2,1
= ... (11)
Y = v
0,1
v
0,2
= v
1,1
v
1,2
= v
2,1
v
2,2
= ... (12)
In other words, X is the frequency difference (in cm
-1
) between all peaks in the
fundamental band (v = 0) and first hot band (v = 1) that correspond to transitions to the
same vibrational state v' in the electronic excited state, and Y is the frequency difference (in
cm
-1
) between all peaks in the first hot band (v = 1) and second hot band (v = 2) that
correspond to transitions to the same vibrational state v' in the electronic excited state.
By matching all peak pairs that define X and all peak pairs that define Y, average
values for both parameters can be obtained. The method for matching the pairs is described
in Snadden's paper. Basically, you are looking for sequential pairs in two bands that give a
relatively constant difference for all pairs. Using X and Y from these data, Eqs. 8 and 10 can
be solved simultaneously to obtain = and _ , the vibrational frequency and anharmonicity
constant for the ground electronic state. Knowing = , the force constant k can be obtained
from Eq. (4). Furthermore, the dissociation energy of I
2
, D
o
, can be estimated as
D
o
= hc= (1 2_ )/4_ ~ hc= /4_ (13)
The relative populations of molecules in any two states separated by an energy A E =
E
b
E
a
, expressed as a fraction, is given by the Boltzmann distribution expression
CHEM 379, Fall 2011 Page 6 of 6
) exp( /
T k
E
N N
b
a b
A
= (14)
Here k
b
is the Boltzmann constant (k
b
= 1.38066 x 10
-23
J K
-1
) and T is the temperature in
Kelvin. Thus, the relative populations of molecules at v = 1 to v = 0 and v = 2 to v = 1 can
be estimated as
) exp( /
0 1
T k
Xhc
N N
b

= and ) exp( /
1 2
T k
Yhc
N N
b

= (15)
Note that in these expressions, k
b
is the Boltzmann constant, not the force constant of I
2
.
Also, note that in Snadden's sample calculation, N
0
:N
1
:N
2
= 1:0.35:0.12, because N
1
/N
0

N
2
/N
1
= 0.35 and (0.35)(0.35) = 0.12.

Laboratory Procedures:

Recording the Spectrum

This experiment will be conducted using the Cary-14 UV-Vis spectrometer. Obtain
the medium-resolution visible absorption spectrum of gaseous diatomic iodine, which
consists of overlapping bands from electronic transitions, each having pronounced
vibrational fine structure. Under the conditions of the experiment, rotational fine structure
cannot be resolved.
Glass sample cells filled with iodine vapor in equilibrium with solid I
2
will be
provided by the instructor. A wavelength scan from 500 nm to 630 nm covers the region of
interest. Each group will generate their own spectra and assign peaks. If additional data is
needed from other groups, then it will be necessary to average all of the relevant peak values.

Calculations
1. Carry out an analysis of the spectrum following the procedure and notation described in
Snaddens paper. Tabulate your data and calculate X, Y, =, _, k and D
o
.
2. Values of X and Y should be quoted with standard deviations, and the consequences of
those confidence limits on calculated values of =, _, k and D
o
should be assessed and
discussed.
3. Compare your calculated values of =, _, k and D
o
with literature values.
4. Estimate the relative populations of the vibrational states v = 0, 1, 2 of I
2
in its ground
electronic state [In carrying out this calculation, note that k is the Boltzmann constant].

1
R. B. Snadden, J. Chem. Educ. 1987, 64, 919-921.