Atomic & Molecular

Spectroscopy Lab

Instruction Manual

Prof. T. Kundu
Anand D. Raut

Department Of Physics
IIT Bombay, Mumbai
 Experiment No. 6

ABSORBANCE SPECTRUM OF IODINE

AIM: Determine the fundamental frequency of vibration, anharmonicity constant and

dissociation energy for the iodine molecule by using the absorption spectra of iodine.

APPARATUS: Source Lamp, Optocoupler, Iodine cell, lens, Optical fibre and Spectrometer,
etc.

THEORY: A molecule possesses many electronic states. There are many vibrational states
corresponding to each electronic state and along with these vibrational states there are many
rotational states. The transitions occur according to selection rules.

Consider two electronic states: a lower (or a ground) electronic states and an upper
(or first excited) electronic state. The vibrational quantum number υ” and those in the upper state
by υ‟. A transition from υ‟ and υ” level is denoted as (υ‟, υ”) and is called as (υ‟, υ”) vibrational
band. For example, a transition from υ‟=0 to υ” =0 is called as (0,0) band. (Corresponding to
these vibrational transitions, there are rotational transitions which appear as degradation to each
vibrational band)

Figure 1- potential energy curve with respect to intermolecular distance, just to show the
Vibration levels in the electronic state.

If a continuous radiation in the visible region is passed through cell containing Iodine vapour a
band spectrum can be seen through a spectrography arising from absorption by iodine molecules
(I 2). This is an electronic transition between the ground state and the excited state as shown in
the figure. The υ” = 0 to υ‟ = 0 known as the 0-0 transition will have the lowest frequency
(highest λ) and can be located near 6200 Å. The other discrete band extend up to about 5000 Å in
the place green region beyond which a continuum can be observed. Since the molecules are at
room temperature, the υ” = 0 is the most populated and most of the observed bands are due to
transitions for υ” = 0 to υ‟ = 0,1,2,3……….The wave number of these bands are denoted by “
00‟ “ 01‟ “ 02‟ “03………” 0D where D denotes the level in the upper state corresponding to
dissociation (This corresponds to the onset of the continuum in the spectrum).

The total energy E of a molecules may be regarded as the sum of the individual
contributions of rotational (Er), vibrational (Ev) and electronic (Ee) energies. That is,

E= Ee + Ev+ Er (1)

[Any interaction between the above energies as well as transitional energy is neglected in Eq. (1)
above]

When expressed in wave number units (cm-1), Eq (1) becomes,

T = Te + G (υ) + F (J) (2)

Here, Te , G (υ) and F(J) are the „TERM VALUES‟ for electronic vibrational and rotational
energies; for example, the vibrational term value is given by :

G (υ) = Eυ /hc = (υ + )ωe - (υ + )2ωe xe + (υ + )3ωe ye +……. (3)

In a transition the wave-number (υ) of one of the spectral lines in by the difference between the
two term values in the upper (T‟) and lower (T”) electronics states, that is:

υ = T‟ – T” = { ( - ) + (G‟ (υ‟) – G” (υ”) } + {Fυ (J‟) - Fυ (J”)} (4)

The representation of the wave-number (υ) of one of the spectral lines in an electronic transition
by means of the value difference is given in Fig.(1) Equation (4) has the form:

υ = υe + υυ + υr (5)

Where the emitted or absorbed wave-number may be regarded as the sum of the electronic,
vibrational and rotational part υυ and υr are the wave numbers corresponding to the vibrational
and rotational energy changes, respectively, and

υe =

υe is the energy difference in cm-1 units between the minima of the upper and lower electronic
states. It remains constant for the
Figure 2- Absorption spectra of iodine molecule.

Each small hump, or peak such as the (26,0) band labelled on the spectrum, corresponds to a
transition between two vibrational levels and is called a band. Each band is comprised of several
hundred lines, each of which involves different upper and lower rotational quantum numbers as
mentioned, these lines are not resolved in the present experiment. The region of maximum
absorption in each band is caused by many of these lines falling together; it is called the band
head.

The set of all of these bands is referred to as the visible band system of Iodine.

Find accurately the λ and 1/λ (=υ) for the bands.

The vibrational energy terms not to the minimum of the potential energy curve where G (υ) = 0
but to the υ = 0 vibrational level where from equation (3) it follows that this vibrational term G
(0) is given by:

G(0) = ωe - xe ωe + ye ωe +…. (6)

The vibrational energy term values are then measured from this G (0) value, which is chosen as
the new zero, and the vibrational term values are represented by the symbol G0(υ) where:

G0(υ) = ω0υ – x0ω0υ2 + y0ω0υ3 (7)

and

G(υ) = G0(υ) + G (0) (8)

The difference between successive levels in the excited state is given by

G(υ+1) - G(υ), which is the wave-number separation of two successive vibrational levels in one
electronic state, is represented by ΔG (υ) where:
ΔG(υ) = G(υ+1) - G(υ) = {G (0) + G0(υ+1)} - {G (0) + G0(υ)}

ΔG (υ) = ω0 – ω0x0 - 2 ω0x0υ (11)

and ΔG (υ) is known as the first difference.

One can plot a graph between G0(υ) and υ. As seen from eqn. (11), the slop of this graph gives -
2 ω0x0υ and intercept on y axis gives ω0 - 2 ω0x0.

When the quadratic expression ω0υ – x0ω0υ2 represents all the vibrational levels correctly. The
dissociation energy of the molecule D0 (in cm-1) is given by

D0 = (12)

Check the second difference Δ2 G (υ) is defined by

Δ2 G (υ) = ΔG(υ+1) - ΔG(υ) = -2 ω0x0 (13)

Δ2 G (υ) is known as the second difference.

Thus, if the analysis is correct, the second difference values for both the upper and lower
electronic states have to give constant values of -2 and -2 respectively. If values are
not roughly constant, then the analysis is unsatisfactory.

PROCEDURE:

To Obtain the visible absorption spectrum of I2 from 500-650 nm using Avantes high resolution
spectrometer that has a resolution of at least 0.2 nm.

1. Place a few crystals of iodine in one of the 10 cm cells, and cap the cell. The vapour
pressure of iodine is sufficient at room temperature to obtain a usable spectrum.
2. Place sample cell in the broad band light path and adjust the focal length of lens to pass
the maximum light through sample cell.
3. Put the collecting lens in front of sample cell and collect the light through multimode
fibre.
4. One end of fibre connects to collimating lens and other end is connected to spectrometer
as shown in figure 4. Heating the cell by wrapping it with heating coil will increase the
intensity of the transitions.
Data Reduction and Analysis:

Figure 2 shows a sample absorption spectrum for iodine. Shown. Assign each peak in the visible
absorption spectrum of iodine to the υ‟‟ = 0 vibrational quantum number labelling the vibrational
state in the ground electronic state in which the transition originated and the ν‟ = 55,54, …15
vibrational quantum number in the excited electronic state. Note that we also see transition
originating and from υ‟ = 1 level of the ground state, as well as transition originating υ‟‟ = 2. As
can be seen from the spectrum, the intensity of these „hot bands‟ swamps the intensity of the
transition originating from the υ‟‟ = 0 state. Note that the assignment of these transitions is
complicated by the fact that transitions originating from the υ‟‟ = 0,1,2 overlap strongly in
portions of the spectrum. In order to correctly make these assignments you will need to refer
given partial assignment in table 1.

Figure 4- Setup for the iodine absorption spectra.

CALCULATION:

1. Draw the Birge-Sponer plot G0 vs ν. Determine the fundamental frequency of vibration (ω0)
and anharmonicity constant (χ0) .

2. Determine the dissociation energy (D0) of iodine molecule. What does the area under the
Birge-Sponer plot suggest.

3. The potential energy of a diatomic molecule can be expressed with the help of Morse potential
function U (r )  D0 [1  exp( (r  Re ))]2 , D0 the dissociation energy, Re is the equilibrium
intermolecular distance, and β is the Morse anharmonicity coefficient (not to be confused with
2 2 r c
anharmonicity constant). Derive the expression for   0 from the Morse potential
D0 * h
function. Where μr=1.053x10-25 kg is the reduced mass of iodine, h is the Planck constant, c is
the speed of light, ω0 if fundamental vibrational frequency, D0 is the dissociation energy.
Determine the value of β.

PRECAUTIONS:

1. If the fiber is not in use than keep the fiber end closed.

2. While taking the reference spectrum, keep the fiber end sufficient away from the lamp so that
spectrometer count won‟t get saturate.

3. Fiber, collimator and spectrometer keep back into the plastic box, once the measurement is
done.
 EXPERIMENT NO: 7

SPIN ORBIT COUPLING

AIM: Determination of spin-orbit coupling constant of and states of copper

and 2P and 2S states of sodium.

APPARATUS: Copper rods, Graduated optical bench, SFAS Mount, Lens, LED,
Objective 20x, Optical fibre, Spectrometer, High voltage power supply, etc.

THEORY AND CALCULATION:

In atomic spectrum, to describe the fine structure, total energy of the atom can be expressed as

E  E 0  E

Where  E represents the perturbation energy due to spin orbit coupling.

E0 unperturbed energy of the atomic state. The perturbation energy due to spin orbit coupling can
be expressed as

 
E  AL, S  L . S

Where L = Total orbital angular momentum

S = Total spin angular momentum

A(L,S) spin orbit coupling constant

  
The total angular momentum, J  L S

 
So , J 2  L2  S 2  2 L. S

J 2  L2  S 2
Or, →L. S =
2

So, the perturbation energy is

 ∆E = A (L,S) [J (J+1) –L (L+1) –S (S+1)] (1)

Now4F notation means (2S+1)L

Where L&S defined earlier.

For example

4=2S +1 So, S= 3/2

and L = 0, 1, 2, 3, 4

S PDFG

So for 4F; L=3

S = 3/2

For 4D; L= 2

S = 3/2

Now value of J according to the coupling of angular momenta

J = |L+S| ….to |L-S|

For 4F J = 9/2, 7/2, 5/2, 3/2

For 4D J = 7/2, 5/2, 3/2, 1/2

Thus due to spin orbit coupling, each level will split into 4 energy levels,
4 4
F F9/2, 4F7/2, 4F5/2, 4F3/2
4 4
D D7/2, 4D5/2, 4D3/2, 4D1/2,

∆E1 and ∆ E₂ can be calculated from eqn. no. 1.

for example:

4 A1
F9/2 ∆E₁ ( ) = [ ( +1) –3(3+1) – ( -1)]
2

= A1
 A1
For 4 ,∆ (7/2) = [7/2 (9/2) – 3.4 – (15/4)] =0
2

and so on

A2
for 4D7/2 ∆E₂ (7/2) = [(7/2) (9/2) – 2*3 – (15/4) ]
2

A2
= [63/4 – 6 – 15/4] = 3A2
2

you construct the energy level diagram by calculating as shown above in term of spin orbit
constants A1 and A2.

The energy diagram,

4𝐹9 2

4𝐹7 2

4𝐹5 2

4𝐹3 2

4𝐷7 2

4𝐷5 2

4𝐷3 2

4𝐷1 2
Now, the electronics transitions which give size to spectrum depends on the selection rule (for
atomic spectra, the electron transition selection rules are)

4𝐹9 2

4𝐹7 2

4𝐹5 2

4𝐹3
2

4𝐷7 2

4𝐷5 2

4𝐷3 2

4𝐷1 2

ΔS =0
ΔJ = 0, ± 1

Total 9 (nine) transitions are possible. The transitions energies, such as

E(1) = E0 +ΔE1 (9/2) – ΔE₂ (7/2) = 1/(in cm-1)

From several observed transitions, we can determine the spin orbit constants for 4F and 4D levels
which are A1 and A2.

It has long been known that the copper spectrum, unlike most spectra, consists of many
spectrum lines half of which are sharp and the other half unusually broad and diffuse. A
thorough investigation of these lines by Allen has showed that the diffuseness is not due to a
pressure or temperature effect but to a natural breadth of the energy levels. Such broad levels
immediately suggest that we are dealing with short mean lives and with the process of the auto
ionization.
 For sodium, transition takes place from 2P3/2→2S1/2 and 2P1/2→2S1/2.

2P3/2

2P

2P1/2
E0
589.0 nm 589.6 nm

2s
2S1/2

LED Alignment:
Copper Spectrum Experimental Set-up:

PROCEDURE:

1. Align the yellow LED with the lens and collimator and get a tight spot at the end of fiber
coupler.
2. Connect one end of fiber to the fiber coupler and other end with the spectrometer.
3. Connect spectrometer with the computer through USB cable.
4. Open the Avantes software and select scope mode (S). Set appropriate integration time
and average value in the software.
5. Make the alignment in such a way so that you can get more than 40000 counts in the
spectrum of yellow LED (at 590 nm).
6. Once you get the spectrum, replace the LED with copper rod .
7. Turn On the supply voltage and short the two copper rods with a third metal rod. You
will observe a green colour light with spark.
8. Collect the spectrum and identify the peak positions (nm) of 9 transitions of copper.
9. Turn off the supply voltage and discharge the copper rod with other metal rod.
10. For Sodium spectrum, remove the fiber from fiber coupler, place it at the bottom of
sodium lamp and collect the spectrum.
PRECAUTIONS:

1. The voltage supply has voltage in the range of 600-700V and current of approximately 1
A. So, always perform the experiment by covering the copper rod with the cover to avoid
any kind of electrical shocks.
2. After finishing the experiment, always discharge the copper rod with third metal rod.
3. While performing the experiment, make sure that fan of power supply should be ON.
4. First close the software and then remove the connection of spectrometer and computer.

Copper Spectrum
4 4 4
4

4 100
4651.13 Å
21494.2 cm-1
22
4 57 U
4704.60 Å
4586.97 Å
21249.9 cm-1
21704.8 cm-1
2
4 21 U 30 U
4797.04 Å
4674.76 Å 4539.70 Å
20840.4 cm-1
2186.60 cm-1 22021.7 cm-1

4 2U 13 U 12
4842.20 Å 4697.49 Å 4509.30 Å
20646.0 cm-1 21282.0 cm-1 22169.8 cm-1
 Experiment No. 8

ROTATIONAL SPECTRUM OF CYNOGEN MOLECULE (C≡N)

AIM: To measure the rotational spectrum of cyanogen molecule using arc spectrometry and
estimate the rotational constant of the molecule.
(1)Record the (0, 0) band at 3883 Å of C≡N molecule.
(2) Determine its:
(a) Rotational constants: (B‟υ and B”υ);
(b) Moment of inertia
(c) The inter-atomic equilibrium distance / bond length for the ground and excited
state.

APPARATUS: Graphite rods, Graduated optical bench, Mounts, Lens, LED, Ojective20x,
Optical fibre, Spectrometer.

THEORY:

Rotational Analysis of diatomic molecules

A molecule possesses many electronic states. There are many vibrational states corresponding to
each electronic state and along with these vibrational states there are many rotational states. The
transitions occur according to selection rules.

Consider two electronic states: a lower (or a ground) electronic state and an upper (or first
excited) electronic state. The vibrational levels in the lower state are denoted by the vibrational
quantum number υ” and those in the upper state by υ‟. A transition from υ‟ to υ” level is
denoted as (υ‟, υ”) and is called as (υ‟, υ”) vibrational band. For example, a transition from υ‟=0
to v”=0 is called as (0, 0) band. Corresponding to these vibrational transitions, there are
rotational transitions which appear as degradation to each vibrational band. The rotational levels
in upper state are denoted by the rotational quantum number J‟ and those in lower state by J”.

The total energy E of a molecules may be regarded as the sum of the individual contributions of
rotational (Er), vibrational (Ev) and electronic (Ee) energies. That is,

E = Ee + Ev + Er (1)

[Any interaction between the above energies as well as translational energy is neglected in Eq 1]

When expressed in wave number units (cm-1), Eq. (1) becomes,

T = Te + G(v) + F (J) (2)

Here Te‟ G(v) and F (j) are the „TERM VALUES‟ for electronic, vibrational and rotational
energies of a molecule. (A „term‟ is defined as the energy value divided by „hc‟. For example,

F(J) =

The rotational term value is given by:

h
F (J )  J ( J  1)  Bv J ( J  1)
8 2 cI (3)

Where I = r 2e is the moment of inertia of the (CN) molecules and  is the reduced mass (cm-1).
Wave numbers of spectral lines arising from transitions between two electronic states (by
emission or absorption) are given by the difference between the two term values for the
corresponding states. Thus,

ν= - =( – ) + ( - ) + ( - ). (4)

Where (') represents the upper and ('') represents the lower electronic state. Or in units of wave
number we can write,

ν= νe + νv +νr (5)

[Note that νv and νr need not be positive in Eq.(5) above.]

E e  E e
Also, Ve  (6)
hc

is the energy difference (in cm-1) between the minima of the upper and lower electronic states. It
remains constant for the two given electronic states. Also, vV  G'G' ' / hc remains constant
for a particular rotational band. Thus, for the wave numbers of the rotational lines alone in a
given vibrational band, Eq. (5)

Simplifies to:

v  ve  vv   F ' J '  F ' ' J ' ' (7)

or v  vo  F ' J '  F ' ' J ' ' , where vo is the band origin.

Substituting for F(J), from Eq. (3) We get:

v  vo  B'V J ' J '1  B' 'V J ' ' J ' '1
(8)

The selection rule for rotational transitions;    

2 2
are

J  J   J   1 (9)

Writing J   J   1 in (8) For R-branch and simplifying we get;

v R J   vo  2BV  3BV  BV J  BV  BV J 2 (10)

Similarly for P branch J  1 , we get on simplification

v p J   vo  BV  BV J  BV  BV J 2 (11)

Note that in (10) and (11) J  has been replaced by J for simplicity and it refers to lower stat only.

The relations (10) and (11) for R and P branches can be represented by a single formula:

v  vo  BV  BV m  BV  BV m2 (12)

Where m = 1, 2, 3, -------- for R branch

m = -1, -2, -3, -------- for P branch

The first and second differences, using empirical relation (8) are given by,

vm   m  1  vm  2BV  2BV  BV m (13)

PROCEDURE:
1. Place the LED, lens, and the optical couplers in the posts, and clamp them onto the optical
bench.
2. Attach one end of the fibre to the SMA type fibre holder and the other to the front side of the
spectrometer.
3. Connect the spectrometer with the desktop using the USB cord provided. The power (LED)
of spectrometer must turn on.
4. Open the Avasoft 8.0 software on the desktop and perform the dark and calibration check
using the mercury light provided.
5. Turn on the LED and align the optical system mentioned in 1 such that you obtain at least
40,000 counts. Note the LED, lens and coupler position from the optical bench.
6. Turn-off the LED and replace it with the graphite rod system (Figure 1).
7. Turn the high power voltage source on and short the positive and negative graphite rods with
a metal-wood rod provided. You should be able to see spectrum within 380-400nm (Figure
2). Record the spectrum and identify the (0, 0) band.
8. Zoom into region between (1, 1) and (0, 0) to identify R and P branches.
9. From mean second difference,  (Equation 13), plot v against m to obtain rotational
constants.
10. Using set of equations in 14, calculate other constants (see Aim 2 b and c).

27.983 10 40

, where I  r 2 With  CN   6.46427 amu.
h h
B   (14)
8 2 cI 8 2 cr
2
I

Figure 1: Setup to measure the cyanogen emission spectrum.

Cyanogen Spectrum Cyanogen Spectrum

(a) (b) (0,0)
(0,0)
Counts (a.u.)

Counts (a.u.)

(1,1)
(1,1)

m=5 m= -5
m=1

386.0 386.5 387.0 387.5 388.0 388.5 387.25 387.50 387.75 388.00 388.25
Wavelength (nm) Wavelength (nm)

Figure 2: (a) Sample (b) Zoomed-in rotation spectrum of cyanogen specifying peak of vibration
band.