NAME: Alizwa Xabanisa

Student Number:23x7997

Title: Absorption band spectra and the dissociation energy of Iodine.

Abstract:

This study explores the visible molecular absorption spectrum of iodine (I₂), a classic
example in molecular spectroscopy due to its well-characterized electronic transitions and
finely resolved vibrational structure. Iodine’s B–X transition system, central to this
investigation, provides insight into the electronic, vibrational, and rotational interactions of
diatomic molecules. By analyzing the absorption spectrum in the 498–621 nm range, we
assigned vibrational quantum numbers to distinct wavelengths and applied polynomial
extrapolation to interpret key spectroscopic parameters. Using the relationships between
vibrational levels and photon energy, we determined the dissociation energies of both the
ground (D₀″ = (1.49 ± 0.02) × 10⁻⁴ J/mol) and excited (D₀′ = (0.149 ± 0.002) × 10⁻⁶ kJ/mol)
electronic states. These values reflect the reduced bond strength in the excited state and
agree qualitatively with theoretical expectations. The vibrational level spacing trend and the
emergence of a continuum at higher energies confirm bond dissociation near the
convergence limit. This experiment not only highlights the quantum mechanical principles
underlying molecular spectroscopy but also reinforces the role of diatomic iodine as a
foundational system in modern laser-based techniques and molecular energy level
modeling.

Introduction:
The iodine molecular spectrum is a prime example of the fundamental properties of
diatomic spectra and was among the first to be successfully investigated. It has a lengthy
visible absorption series linked to the B-X states, which connect with the well-known
atomic fine structure states at great distances. Since the invention of lasers, this spectrum
has continued to be significant in the creation of novel molecular spectroscopic
techniques. Iodine was the first to use optical pumping techniques in molecules and to
develop saturation and polarization spectroscopy; several of its molecular constants are
known with a high degree of accuracy. The electronic-vibrational-rotational levels involved
in the bands are produced by the electronic potential energy curves.[1]

Among these electronically excited levels, the B level is the first one. levels that correspond
to the ground atomic configuration at great separations, aside from the ground X level. The
J-selection rule, the anharmonicity of the lower state, and the difference in the bond
lengths of the B and X states are all immediately supported by the fluorescence spectrum,
which is easier to study than the absorption spectrum. The upper curve shows that an
excited atom I* of energy E(I*) can unite with a normal atom to generate a stable
configuration called B. This and the ground state are involved in the observed light
absorption in the visible range under study. Thus, we use a single prime (') to denote this
state. [1]
The graphic defines the crucial spectroscopic concepts De and D0. The fact that e stands
for "extrapolated" is a helpful memory trick. The difference in energy characteristics
between states X and B is denoted by the letter ve at each electronic level.
The various vibrational levels are displayed and denoted by the numbers v = 0, 1, 2,.... The
distinctive vibrational. The labels "ω" and "to" refer to energies that are wildly inflated in
magnitude.[2] Three of the ten potential molecules of this type—IF, BrF, and C1F—have not
yet been proven to exist, and we have not made an effort to find them using spectroscopy.
We have focused on the other six molecules—Cl2, Br2, I2, BrCl, ICl, and IBr—because the
data for F2 are scant, and only an emission spectrum is known. Except for BrCl, the spectra
of these have been thoroughly examined and partially understood.[3]

The spectrum becomes continuous beyond the convergence limit, indicating

photodissociation that produces atoms with continually fluctuating kinetic energy
levels.[2]

Iodine vapour is violet because it absorbs red, yellow, and green radiation in the electronic
excitation and the formation of iodine atoms on absorption of radiation of sufficient energy.
Spectroscopic examination of the absorption spectrum, Fig. 2. It consists of a number of
progressions of lines due to various vibrational transitions superimposed on the electronic
transitions. It can be observed that the absorption of light intensity is at about 537.0.

`
Fig 1. The Iodine Vapour Absorption Spectrum. (From https://stevesopenlab.fr/the-
iodine-absorption-spectrum-part-ii/)

The I2 Spectrum (Fig. 2) can be interpreted in terms of diagrams of potential energy against
internuclear distance for the ground state, I2, and I2 for the excited state I2*, molecules,
Fig. 3. The curves show the allowed vibrational energy levels, with quantum numbers v '' in
the excited state.

Fig 2: Vibrational quantum number of the upper electronic levels

Fig 3: Electronic and vibrational transitions for the I2 molecule.

As v′ increases, the vibrational energy spacing decreases. At the upper edge of the well, the
vibrational energy spacing decreases to 0, which means that the energy forms a continuum
rather than being quantized. It is at this limit that bond dissociation occurs. The energy
required to dissociate the bond is actually D′o rather than D′e because the molecule
cannot have less than the zero-point energy.

Method:

1. We first extracted the data for the wavelength from the Excel graph that was provided
and then proceeded to assign vibrational frequencies to the wavelengths.

2. We then calculated the change in wavelengths and the mean wavelength, after which we
plotted the δλ vs λ graph and then extrapolated the points using a trendline, which was a
polynomial graph.

3. We then proceeded to plot another graph of λ vs v, then extrapolated the graph using a
polynomial trend line.
𝐿ℎ𝑐
4. Then we calculated the Energies using the intercepts of the graphs using 𝐸 = ,
𝜆

Then determine D’0 and D”0.

Results:
Graph 1: The graph of λ vs v.

Wavelength vs vibrational frequency

580
570
560
Wavelength

550
540
530
520
510
500
0 10 20 30 40 50 60
y = 0.0299x2 - 3.7564x + 621.05 Vibrational frequency
R² = 0.9995

From the graph, we were able to determine the wavelength of λ0 =621.05± 6nm. Then we
were able to determine the E0= (1.93±0.02)×10-4J/mol .Then we determined the energy of the excited
state at 1316nm, which was Ea = (9.09±0.04)*E-05 j/mol. Then we determined D’0 = (0.149±0.002)
×10-6 KJ/mol.

Mean wavelenghth vs change in lamda

570

560
Mean wavelength

550

540

530

520

510

500
0 0.5 1 1.5 2 2.5 3
Change lambda y = 4.3306x2 + 9.4763x + 498.28

R² = 0.9904

Graph 2: λ vs δλ graph
From the graph, we were able to determine the wavelength of the lowest energy level λc =
498.28 ±6nm. Then we determined the energy Ec =(2.4 ±0.03)×10-4 J/mol. Then we determined D’’0
=(1.49±0.02)×10-4 J/mol.

Discussion:
From the experimental data, the dissociation energy of the excited state (D0′) was determined to
be (0.149±0.002)×10−6 kJ/mol, which converts to (1.49±0.02)×10−4 J/mol, while the dissociation energy of
the ground state (D0′′) was found to be (1.49±0.02)×10−4 J/mol. These values were derived from the analysis
of λ vs. v and λ vs δλ graphs, where the respective wavelengths and corresponding energies were calculated.
The obtained D0′′ value agrees reasonably well with typical literature values for small diatomic molecules,
which generally range between 1.5×10−4 J/mol and 5×10−4J/mol, though it falls on the lower end, possibly
indicating a weakly bound state or experimental uncertainties. Potential sources of error include the
uncertainty in λc (±6 nm), approximations in the theoretical model (e.g., Morse potential or Birge-Sponer
extrapolation), and instrumental limitations in measuring δλ. The fact that D0′ is significantly smaller
than D0′′ is consistent with expectations, as excited states typically have lower dissociation energies. For a
more precise comparison, referencing a specific literature value for the molecule under study (e.g., I2)
would strengthen the analysis. Overall, the results are internally consistent and align with theoretical
predictions, though further refinement could reduce discrepancies.

References:
1.Durie, R. A. (1951). The visible emission spectra of iodine and bromine monofluorides
and their dissociation energies. Proceedings of the Royal Society of London. Series A.
Mathematical and Physical Sciences, 207(1090), 388-395.

2. Curtis, W. E., & Evans, S. F. (1933). The spectra of the halogen molecules. Part I.-
Iodine. Proceedings of the Royal Society of London. Series A, Containing Papers of a
Mathematical and Physical Character, 141(845), 603-625.

3. Stafford, F. E. (1962). Band spectra and dissociation energies: A physical chemistry

experiment. Journal of Chemical Education, 39(12), 626.

4. Department of Chemistry, Rhodes university: Physical Chemistry III Practical manual

5. https://stevesopenlab.fr/the-iodine-absorption-spectrum-part-ii/)