Experiment 5

Molecular Spectroscopy
Introduction
Molecular spectroscopy is the study of the interaction of electromagnetic radiation
with molecules. Electromagnetic radiation is customarily divided into different regions
reflecting the different types of molecular processes that can be caused by such radiation.
The classifications of electromagnetic radiation that can be used in the optical spectroscopy
are summarized in Table 1. The absorption of microwave radiation generally causes
transitions between rotational energy levels; the absorption of infrared radiation generally
causes transitions between vibrational levels and is accompanied by transitions between
rotational energy levels; and the absorption of visible and ultraviolet radiation causes
transitions between electronic energy levels, accompanied by simultaneous transitions
between vibrational and rotational levels.
Table 1. Regions of the electromagnetic spectrum and the corresponding molecular
processes.
Visible and
Region Microwave Far Infrared Infrared
Ultraviolet
Frequency/Hz 109−1011 1011−1013 1013−1014 1014−1016
Wavelength/m 3x10-1−3x10-3 3x10-3−3x10-5 3x10-5− 6.9x10-7 6.9x10-7− 2x10-7
Wavenumber/cm-1 0.033−3.3 3.3−330 330−14500 14500−50000
Energy/J.molecule-1 6.6x10-25− 6.6x10-23 6.6x10-23− 6.6x10-21 6.6x10-21− 2.9x10-19 2.9x10-19−1.0x10-18
Rotation of
Rotation of small Vibrations of Electronic
Molecular Process polyatomic
molecules flexible bonds transitions
molecules
The most primitive model to describe the motion of a vibrating diatomic molecule is the
1
harmonic oscillator model, for which the potential energy is 𝑉(𝑥) = 2 𝑘𝑥 2 . The allowed
energy levels, calculated from the Schrödinger equation, are
1
𝐸(𝜈) = (𝜈 + 2) ℎ𝑐𝜔 ̃𝑒 (1)
Where 𝜔 ̃𝑒 is the fundamental vibrational frequency in cm–1, h is Planck's constant, c is the
speed of light, and v, the vibrational quantum number, has values 0, 1, 2, 3,...
For a rotating diatomic molecule, the rigid rotor is a useful model; with the rigid rotor
approximation, the molecule is considered as two masses held by a rigid, massless rod. The
solution of the Schrödinger equation yields:
h2
E ( J ) = J ( J + 1) 2 = J ( J + 1) Be h
8 I (2)
where the rotational quantum number, J, takes on integral values 0, 1, 2..., 𝐵̃𝑒 is the
rotational constant in cm−1, and I is the moment of inertia given by:
I = Re 2
(3)
where Re is the internuclear distance and  is the reduced mass of the molecule (NA is
Avogadro's number):
mm 1
= 1 2
m1 + m2 N A
Real molecules undergo simultaneous rotational and vibrational motion, and the energy
𝐸(𝜈, 𝐽) might be considered to be a sum of rotational and vibrational contributions.
However, the simple harmonic oscillator and rigid rotor models are not sufficient to
describe the spectra of molecules at very high resolution. A more complex expression for
the energy is necessary to describe the true molecular motion of a diatomic molecule. The
energy values, E/hc (in cm−1), are:

T (v, J ) = e (v + 1 2) − e  e (v + 1 2) 2 + Be J ( J + 1)
harmonic anharmonicity rigid rotor

− De J ( J + 1) −  e (v + 1 2 ) J ( J + 1)
2 2

cetrifugal distortion vibrot coupling

(4)
where all quantities are in cm−1. The first and third terms are simple harmonic oscillator
̃𝑒 and 𝐵̃𝑒 are in cm−1. The second term is
and rigid rotor energies, respectively. Note that 𝜔
the anharmonicity correction, which is a measure of the deviation of the potential energy
1
from the simple parabola predicted by 𝑉(𝑥) = 2 𝑘𝑥 2 . The fourth term is the centrifugal
distortion that corrects for the fact that the rotor is not a rigid rod, but a bond that can
expand and contract. This term will be ignored since it is only important at very high J
values. The last term is the coupling of vibration and rotation. During vibration, R changes
therefore 𝐵̃𝑒 changes and so the two motions are not totally independent as we originally
assumed.
The selection rules for the molecular motion within the harmonic oscillator and
rigid rotor approximations are v = 1 and J = 1. For anharmonic motion, v can also
be 2, 3…. The v = 1 transition is the fundamental and the 2, 3 transitions are called
overtones. Since the molecule is absorbing vibrational energy, v = +1. However, J can
be either +1 or –1 (see Figure 1). When J = +1 the transition is called an R branch; J = –
1 (higher wavenumber) is a P branch transition (lower wavenumber).

Figure 1. The rotational energy levels, J, imposed on vibrational energy levels, . The
transitions between levels that would result in the P- and R-branches are depicted in left
and right, respectively, in addition to the theoretical Q-branch line in the middle.
This change in vibrational energy (ν = 0 to ν = 1) with several different rotational
energy changes (J = ±1) leads to the splitting in a typical ro-vibrational spectrum shown in
Figure 2. The peaks to the right correspond to what is called the “P-Branch,” where ΔJ =
−1, and the peaks to the left correspond to the “R-Branch,” where ΔJ = +1.
 Figure 2. Typical appearance of a ro-vibrational FTIR spectrum
Experimental Part
A diagram depicting the manifold used for the production of the HCl and DCl gases is
shown below in Figure 3:

Figure 3 – Vacuum manifold for HCl experiment

The manifold is relatively straightforward in use. Numbers 1-5 are stopcocks. The pump
trap was a trap that a thermos filled with liquid nitrogen surrounded to condense any gas-
phase HCl before it reached the vacuum pump. After closing all stopcocks, the pump was
turned on, and stopcock one was opened to pump the system down in pressure to 1 torr.
Stopcock 1 was closed, and the pressure slowly rose, indicating a leak. This was found to
be at the junction from the gas generator to stopcock 5. This was repeatedly checked
throughout the experiment to ensure proper sealing of the system. Once the leak was fixed,
the system pumped, and the reading stayed steady at 1 torr, stopcocks 3 and 4 were opened
to pump out the IR gas cell. Once this also reached 1 torr, stopcocks 3 and 4 were closed,
and it was removed and used to create a background spectrum in the FTIR instrument. This
background FTIR spectrum was collected at both 16 cm-1 and 1 cm-1 resolution. The IR
cell was reconnected to the manifold, and the rest of the experiment began. The main part
of the experiment was divided into two halves–first, the production of HCl and the
associated FTIR analysis, and then the production of DCl and its associated FTIR analysis.
 Report
Molecular Spectroscopy
Hint: You can use extra sheets

Name: Partners’ Names:

Abstract
Introduction
Experimental Details
Data Sheet

Figure 4. The HCl Spectrum in the Mid-Infrared Spectrum.

From the observed vibrational-rotational lines for the  = 0 to  = 1 transitions, Determine 𝐵̃𝑜 , 𝐵̃1 , 𝐵̃𝑒 , 𝛼̃𝑒 , 𝐼̃𝑒 𝑎𝑛𝑑 𝑟𝑒 for H35Cl.
Discuss the isotope effect with reference to H35Cl
Figure 5. The Ro-Vibrational Mid-IR Spectrum of H35Cl in a Viewable Range for the Overtone Transitions.
Do similar Calculations.
Calculations
Results
Discussion
Conclusion
References