LECTURE 7 (B)

SPC 2205: THEORY OF SPECTROSCOPIC TECHNIQUES

QUESTIONS AND ANSWERS

Answer
Raman spectroscopy is a vibrational spectroscopic technique based on the inelastic scattering of
monochromatic light (usually from a laser). When this light interacts with a sample, most
photons are scattered elastically (Rayleigh scattering), while a small fraction is scattered
inelastically. These inelastically scattered photons gain or lose energy corresponding to
molecular vibrational transitions, and the energy shifts—reported in wave numbers—form the
Raman spectrum.

Question 2
Differentiate between Stokes and Anti-Stokes lines in a Raman spectrum.

Answer
Stokes lines occur when incident photons lose energy to the sample, resulting in scattered light
with longer wavelengths (lower energy). Anti-Stokes lines appear when photons gain energy
from the sample, producing scattered light with shorter wavelengths (higher energy). These shifts
provide insights into the vibrational energy levels of the molecules.

Question 3
Why are symmetrical vibrational modes often strong in Raman spectra but weak or absent in
infrared spectra?

Answer
Symmetrical vibrational modes do not produce a significant change in dipole moment, making
them weak or inactive in infrared spectroscopy, which relies on dipole changes. However, these
modes often cause a notable change in polarizability, making them strongly Raman active and
clearly observable in Raman spectra.

Question 4
How is the position of Raman spectral lines typically reported, and what does this unit
indicate?
Answer
The positions of Raman spectral lines are reported in wave numbers (cm⁻¹). This unit indicates
the energy difference between the incident and scattered light, directly correlating to the
vibrational energy transitions within the molecule.

Question 5
What role does the laser play in Raman spectroscopy?

Answer
The laser serves as the monochromatic light source in Raman spectroscopy. It illuminates the
sample, and its consistent wavelength is crucial for generating clear Raman scattering. The
laser's light interacts with the sample, and the resulting energy shifts in the scattered light reveal
information about the sample's vibrational and rotational modes.
Question 6
Explain the basic experimental arrangement for Raman spectroscopy. What is the role of the
light source and the detector in this setup?

Answer
The experimental arrangement in Raman spectroscopy involves passing monochromatic light—
commonly from an argon-gas laser—through the sample. The light interacts with the molecules
and is scattered in different directions. A key component is the detector (typically set at a right
angle to the incident beam), which collects the scattered light. The spectrometer then analyzes
the light to detect slight shifts in wavelength. These shifts occur because, during the interaction,
the incident photons temporarily transfer energy to the molecules (or vice versa), causing
changes in their vibrational and rotational energy levels. The resulting scattered light, with its
shifted wavelengths, is reported in wave numbers (cm⁻¹) and forms the Raman spectrum.

Question 7
Discuss how Raman spectroscopy can provide information on molecular symmetry. How do
the selection rules differ from those in infrared spectroscopy?

Answer
Raman spectroscopy is particularly useful for studying molecular symmetry because its selection
rules are based on changes in polarizability rather than changes in dipole moment (as in infrared
spectroscopy). For a vibrational mode to be Raman active, the molecule must experience a
change in polarizability during the vibration. This allows even symmetric vibrations (which may
not involve a change in dipole moment) to be observed in Raman spectra. For example, in
molecules like ethene, the symmetric double-bond stretching vibration does not appear in the IR
spectrum due to the absence of a dipole moment change, but it appears strongly in the Raman
spectrum because the vibration causes a significant change in polarizability. This complementary
behavior helps in determining the symmetry and structure of the molecule.

Question 8
Why might a symmetric molecule such as diatomic oxygen (O₂) be Raman active but not
infrared active? Explain using the underlying physical principles.

Answer
In infrared spectroscopy, a vibrational transition is observable only if there is a change in the
dipole moment of the molecule. Diatomic oxygen (O₂), being a symmetrical molecule, does not
exhibit any change in dipole moment during vibration, so it is inactive in the IR region.
However, Raman spectroscopy is based on the change in polarizability of the molecule. Even if
the molecule is symmetric and lacks a dipole moment change, its electron cloud may still
become more or less polarizable as it vibrates. Therefore, O₂ can produce a Raman signal despite
being IR inactive. This difference in selection rules allows Raman spectroscopy to detect
vibrational modes that infrared spectroscopy cannot.

Question 9
Compare the Raman and infrared spectra of tetrachloroethene as discussed in the document
(refer to lecture notes). What does the comparison reveal about the vibrational transitions in
this molecule?
Answer
The document describes that in tetrachloroethene, the stretching vibration of the double bond
appears very strong in the Raman spectrum but is either very weak or completely absent in the
infrared spectrum. This observation is a direct result of the molecule's symmetry. In
tetrachloroethene, the double-bond stretching vibration is symmetrical, meaning it does not
involve a significant change in dipole moment—hence, it is weak or not observed in IR
spectroscopy. However, the same vibration induces a change in polarizability, making it Raman
active and thus strongly visible in the Raman spectrum. This comparison underlines the
complementary nature of the two spectroscopic techniques and how Raman spectroscopy can
reveal information about symmetrical vibrations that infrared spectroscopy misses.

Question 10
Describe the process by which a Raman spectrum is generated. How are the observed shifts in
wavelength interpreted?

Answer
A Raman spectrum is generated when a sample is illuminated with monochromatic light (usually
from a laser). Most of the light is scattered elastically (Rayleigh scattering), meaning it has the
same energy (or wavelength) as the incident light. However, a small portion of the light is
scattered inelastically (Raman scattering). In this process, photons interact with the molecules,
exchanging energy with the vibrational or rotational states of the molecules.

• Stokes scattering: If the photon loses energy to the molecule, the scattered photon has a
longer wavelength (lower energy) than the incident light.

• Anti-Stokes scattering: Conversely, if the photon gains energy from the molecule, it
appears at a shorter wavelength (higher energy).

The shifts in wavelength (or wave numbers) correspond directly to the energy differences
between the molecular vibrational or rotational states. By measuring these shifts, one can infer
the vibrational energies and thus gain insight into the molecular structure and bonding.

Question 11
Explain why nearly symmetrical molecules like cyclohexene might show differences in their
infrared and Raman spectra. Provide an example based on the document.

Answer
Nearly symmetrical molecules, such as cyclohexene, display differences in their infrared and
Raman spectra because the two techniques respond differently to vibrational modes. In
cyclohexene, certain vibrational modes are only weakly IR active because the associated
vibrations involve a small change in the dipole moment due to near symmetry. However, these
same modes can be more prominent in the Raman spectrum if they involve significant changes in
polarizability. For instance, while the double-bond stretching vibration may be weak in the IR
spectrum (owing to minimal dipole change), it is slightly stronger in the Raman spectrum due to
the more pronounced change in polarizability. This distinction helps in confirming molecular
symmetry and provides a fuller understanding of the vibrational dynamics of the molecule.