The Electronic Absorption Spectrum of Iodine

Aim
Analyse the fine vibrational structures of its electronic excited state upon measuring the electronic
absorption spectrum of iodine using UV-visible spectrometer.

Results and Calculation
The peaks are identified as follows:
Wavelength
(nm)
Frequency
(cm
1
) v" v'
Wavelength
(nm)
Frequency
(cm
1
) v" v'
627.85
15927.3712 2 5
558.8
17895.4903 0 20
619.3
16147.263 2 6
557.25
17945.2669 1 23
614.85
16264.1295 2 7
556
17985.6115 0 21
612.2
16334.5312 2 8
554.65
18029.3879 1 24
610.7
16374.652 2 9
553.3
18073.3779 0 22
606.65
16483.9693 2 10
552.85
18088.089 1 25
602.95
16585.1231 2 11
550.65
18160.3559 0 23
599.3
16686.1338 2 12
548.85
18219.9144 1 26
595.6
16789.7918 2 13
548.05
18246.5104 0 24
591.8
16897.6005 2 14
547.3
18271.5147 1 27
588.25
16999.575 2 15
545.55
18330.1256 0 25
584.8
17099.8632 2 17
543.9
18385.7327 1 28
581.3
17202.8213 2 18
543.2
18409.4256 0 26
580.9
17214.6669 1 15
540.9
18487.7057 0 27
578.1
17298.0453 2 19
538.75
18561.4849 0 28
577.45
17317.5167 1 16
536.7
18632.3831 0 29
574.75
17398.8691 2 20
534.6
18705.5743 0 30
574.3
17412.5022 1 17
532.65
18774.0543 0 31
571.2
17507.0028 1 18
530.7
18843.0375 0 32
568.2
17599.4368 1 19
528.85
18908.9534 0 33
567.45
17622.698 0 17
527.15
18969.9327 0 34
565.4
17686.5936 1 20
525.45
19031.3065 0 35
564.45
17716.3611 0 18
523.8
19091.2562 0 36
562.65
17773.0383 1 21
522.3
19146.0846 0 37
561.6
17806.2678 0 19
520.75
19203.0725 0 38
559.9
17860.3322 1 22
519.4
19252.9842 0 39
517.95
19306.8829 0 40
510.05
19605.921 0 47
516.7
19353.5901 0 41
509.05
19644.4357 0 48
515.45
19400.5238 0 42
508.2
19677.2924 0 49
514.25
19445.7948 0 43
507.4
19708.3169 0 50
513.05
19491.2777 0 44
506.5
19743.3366 0 51
512
19531.25 0 45
505.9
19766.7523 0 52
510.95
19571.3866 0 46
504.65
19815.7139 0 53



By plotting against and performing a Regression analysis of it, we obtain
Te' - Te" 15917.768
ve' 121.41006
ve'xe' 0.8645886
ve" 241.01751


Figure 1: A modified Birge-Sponer plot to determine the frequency at equilibrium and the
anharmonicity constant.

From the graph, the equation of the best-fit line is found to be y = -1.8805x + 128.62.
ee = -1.8805 (-2) = 0.9403 cm
-1

e = 128.62 + 0.9719 = 129.6 cm
-1

e = 0.9719 129.6 = 7.499 x 10
-3

D0 = = 4401 cm
-1

De = = 4466 cm
-1

= [(127 x 127) (127 + 127)] x 1.67 x 10
-27
kg = 1.060 x 10
-25
kg (4 s.f.)
Given that e =

, k = (2ce)
2
= 64.83 Nm
-1

vmax = - = - = 67 (integer)

A comparison between the observed and model frequency is as follows:
y = -1.8805x + 128.62
0
10
20
30
40
50
60
70
80
90
100
0 10 20 30 40 50 60

G
(v' +0.5)



Figure 1: A plot of observed versus model frequency to determine the clones that the model
approximates experimental values.

Discussion
Traditional IR spectroscopy and UV/VIS spectroscopy normally provide very different
types of molecular information due to their large differences in available light energy.
The IR part of the optical spectrum only provides enough energy to look at the
relatively low-energy transitions from one vibrational level. It does not have enough
energy to induce an electronic vibration. In the case of UV/VIS spectroscopy,
however, the incident photons are much higher in energy than in IR. Because of this
additional energy there is now enough energy to excite the molecule from its
ground electronic state to a higher electronic state (depending on the specific
system). This gives rise to what is generally a broad absorption peak in the UV/VIS
region of the spectrum.

This transition from ground to excited electronic states does not occur in isolation
however. One reason that the UV/VIS absorption spectrum is usually so broad is that
in the process of inducing an electronic transition, there is still enough energy to also
simultaneously excite various vibrational levels in that excited electronic state. The
result is that there is a fine structure due to vibrations thatcan be sometimes be seen
along with the electronic spectrum. We refer to this combination of vibrational and
electronic transitions as generating a vibronic spectrum.


y = -0.0052x + 17130
R = 0.8274
0
5000
10000
15000
20000
25000
-800000.0 -600000.0 -400000.0 -200000.0 0.0 200000.0


The simplest quantum mechanical model for the vibration of a diatomic molecule is
the harmonic oscillator. In this model,the potential energy is parabolic.

The energy of a harmonic oscillator is:

The fundamental vibrational frequency, (e, is used to define the energy gap between
each evenly-spaced vibrational level and is given by:

k is the force constant (in N/m) and is the reduced mass of the molecule. The
harmonic oscillator is a reasonable model for molecular vibration at very low
energies, but it does not account for a very important property the dissociation of
the molecule at large distances (or energies).

Morse Potential
The simple harmonic oscillator has a parabolic potential and the molecules energy
can rise indefinitely; there is no upper limit to the parabola. A better model for the
potential energy of a diatomic molecule was proposed by P. M. Morse in the later
1920s. The Morse potential is a superior model because in the Morse potential, the
molecule can dissociate if its vibrations get too large.

The form of the Morse function is:

In this equation, De is the dissociation energy of the molecule (measured from the
bottom of the potential curve to where the curve levels off), re is the equilibrium bond
length of the molecule and is the Morse parameter. The dissociation energy, De, is
defined as the energy necessary to dissociate the molecule when measured from the
bottom of the potential energy well. It is slightly larger than the bond energy, Do,
which is measured from the lowest vibrational energy.

The ground state and each excited state have their own individual Morse curves.
These curves have different dissociation energies, equilibrium bond lengths and
curvature as you can see from the next figure.
Another difference between the Morse curve and the simple harmonic oscillator is
the energy pattern. In the harmonic oscillator, the energy levels are equally spaced
while for the Morse potential, the energy expression is:



The term (exe is the anharmonicity constant. It measures the deviation of the Morse
curve from the ideal harmonic oscillator. Because of the quadratic anharmonicity
term, the spacing between vibrational levels in the Morse potential are no longer
evenly spaced like they are with the ideal harmonic oscillator.
UV-Visible Spectroscopy



UV-visible spectroscopy makes use of the fact that energy, in the form of photons, can be absorbed
from light by a particular compound to excite an electron from its ground state to a molecular orbital
of higher energy level. Most of the time, it is the transition of electrons from the highest occupied
molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). The molecular orbitals
in molecules are of three types, bonding ( or ), non-bonding (n) and anti-bonding (* or *).
Electrons, in their ground state, are normally present in the bonding orbitals. Lone pairs of electron
reside in the non-bonding orbitals. The higher energy orbital to which they are promoted is almost
invariably an anti-bonding orbital. There are only three types of electron transitions that can produce
absorption in the UV-visible region: *, n * and n *. Thus, only molecules with and n
electrons can give rise to characteristic absorption spectra in UV-visible spectroscopy (ChemGuide,
2007 [A1]). When the energy of photons corresponds to the energy gap between two particular
molecular orbitals, the electron absorbs the energy. The energy of a photon of light can be described
using the equation below.

hc
hv E = =

In the equation above, E is the energy (J), h is the Plancks constant (~6.626 x 10
-34
J/s), is the
frequency (s
-1
), c is the speed of light (~3.0 x 10
8
m/s) and is the wavelength of light (m).

Besides that, through the use of Beer-Lamberts Law shown below, UV-visible spectroscopy can also
be used to analyse quantitatively how much of a compound is present in the sample as it shows that the
absorbance value at a particular wavelength is proportional to the concentration of the molecule studied
(Thomas, 1996 [B1]).
l c
I
I
A . . lg
0
c = |
.
|

\
|
=

In the equation above, A is the absorbance, I0 is the intensity of incident radiation approaching the
solution, I is the intensity of emerging radiation, is the molar absorptivity (a measurement of how
strongly a chemical species absorbs light at a given wavelength), c is the concentration of the compound
studied and l is the path length of the cell used.

In employing the UV-visible spectroscopic method for analysis, it is important to first zero the
background absorption, i.e. absorption that comes from the environment without the sample being
studied. The gas cell is initially inserted into the UV-visible spectrometer, the wavelength set to 640nm
to 500nm and the absorption zeroed in order to prevent inaccuracies when measuring the absorption of
iodine vapour afterwards. This is then followed by the measurement of the iodine vapour by inserting
approximately 1 g of iodine crystals into the cell. Since iodine crystals are able to sublime at room
temperature, there is no extra treatment required to produce the iodine vapour that is going to be
measured. A few shakes of the gas cell are enough to bring about the sublimation process. The cell is
again inserted into the UV-visible spectrometer, and the absorption is scanned (at the same range of
wavelengths from 640nm to 500nm).



It is important not to keep the wall of the gas cell clear, e.g. not to touch the wall where light is going
to pass through during the spectroscopic analysis. Fingerprints left on the wall may result in
inaccuracies of the absorbance readings obtained. Besides that, it is also important to keep the inside of
the cell dry. As the amount of iodine crystals added is small, this means that the concentration of the
iodine vapour is small. The presence of water inside the cell may result in absorption peaks that are
indistinct possibly due to the interactions between water and the iodine vapour which is in the excited
state. In addition, the presence of any impurities inside the cell would result in deviations from the
Beer-Lamberts Law which will cause the absorbance readings to be inaccurate.

However, in this experiment, the R
2
value of the best-fit Birge-Sponer plot obtained is 0.9929 which is
close to unity. Hence, the plot can be considered as linear and thus the parameters obtained from the
graphical method can be regarded as reliable. Should there be more time for the experiment, a repeat
should have been done in order to ensure the reproducibility of the results obtained.

UV-Visible Spectrum

In the spectrum obtained, one of the most striking features are the overlapping progessions of the peaks,
which is due to the fact that the selection rule for vibrational quantum number, v, is not limited to v
= 1 due to anharmonicity. Anharmonicity is defined as the deviation of a system from being a
harmonic oscillator. In addition to the fundamental bands where v = 1, there are other bands, known
as the overtone bands, which occur in the spectrum from v = 2, 3, etc. transitions. Another
important point to note is that the peaks get progressively broader (and the distances between the peaks
also get larger) towards longer wavelengths. The reasons for this phenomenon will be discussed in the
Exercise section. Also, the resolution of the spectrometer is insufficient to resolve the rotational peaks
within each vibrational peak, causing the rotational peaks to be merged together. A consequence to
unresolved rotational peaks is that the spectrum appears to be asymmetrical.

It can also be observed that the vibrational lines are of varying intensities. As the intensity of a particular
band rise to the maximum, that of the other band adjacent to it decreases to a minimum. The Franck-
Condon principle states that an electronic transition takes place so rapidly that a vibrating molecule
does not change its internuclear distance appreciably during the transition (Banwell, 1983 [B2]).
According to the principle, the most probable transitions are those having the greatest values in the
expression where the intensity of a vibronic transition is proportional to the overlap integral between
the vibrational wavefunctions of the two involved states (the ground state and the excited state). The
most probable transitions involve a more significant overlap between the wavefunctions of both states.
The larger the value of the overlap integral, the higher the intensity of the peak as the two parameters
are directly proportional to one another. Hence, the transition probability and the electronic transition
intensity are governed by this principle.

Another important point to note is that at wavelengths starting from approximately 503nm, the peaks
seem to appear as a continuum which may indicate the point of dissociation of the iodine molecule


after it reaches the maximum vibrational energy level. However, from the calculation of vmax, the
maximum value is found to be 67. Since peak no. 71 corresponds to the v = 57 as shown in Table 2
and there are less than 10 small peaks observed between 500nm and 503nm, it can be conjectured that
continuum will only be reached below 500nm.

Colour of Iodine


Figure 2: Colour
Wheel
When white light passes through a coloured substance, a characteristic
portion of the wavelengths is absorbed. The remaining light will then
assume the complementary colour to the wavelengths absorbed. This can
be illustrated using a colour wheel. Iodine vapour absorbs mostly the
wavelengths corresponding to the yellow light, thus we perceive the
colour of the vapour to be purple.

Other Concerns

Considering the electronic configuration of the iodine molecule (which can be found in the Exercise
section), electronic excitation that is caused by the visible light irradiation results in a pair of electrons
in the 5pg* molecular orbital to be promoted to the higher energy 5pu* molecular orbital, a more anti-
bonding molecular orbital. This phenomenon results in the decrease of the I-I bond strength and the
subsequent increase in the I-I bond length.

The difference between the two dissociation energy parameters (D0 vs De) is that D0 describes the
difference in the energy between the energy level at the point of dissociation of the molecule and the
zero point energy of the molecule, whereas De describes the energy of dissociation obtained from the
bottom of the well of the potential energy curve.

Even though there is only one chemical used in this experiment, which is iodine, it must be handled
with care since it may pose health risks. Iodine itself is toxic so that it may be fatal when inhaled as it
can be damaging to the mucous membrane and the respiratory tract. Solid iodine can sublime at room
temperature. Hence, it is important to ensure that the experiment is done in a well-ventilated
environment. As the vapour can also be irritating to the eyes, goggles must be worn at all times to
prevent the iodine vapour from coming into contact with eyes. In addition, gloves should be worn when
iodine is added into the gas cell in order to prevent contact with the skin. As such, safety precautions
need to be observed at all times during the experiment to prevent unnecessary accidents.


B State Dissociation Energy. Note that the area under the Birge-Sponer plot equals the
dissociation energy '0~D which is related to the equilibrium dissociation energy '~eDby the zero
point energy


Precautions Taken, Sources of Error and Improvements
The amount of iodine placed in cell should be small to prevent excess, which would otherwise shift the
region of absorption of the Beer-Lambert Absorption plot near the plateau. This means the
concentration is too high. As such, only a small amount is used, but the cell is shook vertically until a
distinct light violet colouir against a white background can be observed.
The shaking of the cell too should not be perfectly horizontal, as that risk solid iodine to be stuck on
the salt window that would interfere with the absorption spectrum. In this experiment, we had shaken
it vertically.

Conclusion
From the spectrum obtained, as well as with the aid of graphical methods, the experimental values are
determined to be as follows: e = 129.6 cm
-1
, e = 7.449 x 10
-3
, D0 = 4401 cm
-1
and De = 4466 cm
-1
,
corrected to 4 significant figures.

References
1. McNaught, I. J., J. Chem. Ed., 57, 101-105 (1980)
2. Gaydon, A. G., Dissociation Energies, Chapman and Hall, London, 2nd Ed., Rev., 1953.