PHYSICAL CHEMISTRY :

1. Quantum Chemistry

2. Chemical Bonding

3. Molecular Spectroscopy

Molecular Spectroscopy :

1. Rotational Spectroscopy

2. Vibrational Spectroscopy

3. Raman Spectroscopy

4. Electronic Spectroscopy

5. NMR Spectroscopy

6. ESR Spectroscopy

• Molecular Spectroscopy: deals with the study of the electromagnetic waves and matter.

• Spectroscopy can tell us the structure of matter.

• A molecule in space can possess:

 Rotational energy by virtue of bodily rotation about its centre of gravity.

 Vibrational energy due to the periodic displacement of its atom from their equilibrium
position.

 Electronic energy since the electrons associated with each atom or bond are in unceasing
motion, etc.

 A molecule can exist in a variety of rotational, vibrational, etc energy levels and can
move from one level to another only by a sudden jump involving a finite amount of
energy.

 Spectroscopy deals with the transitions that a molecule undergoes between its energy
levels upon absorption of suitable radiations determined by quantum mechanical
selection rules.

 Quantum mechanics tells that the energy levels of all the systems are quantized and are
designated by the appropriate quantum nos. These energy levels are obtained by the
solutions of the time- independent Shrodinger equation.
How does a spectrum arises?

• If a photon of frequency  falls on a molecule in the G.S. & its energy is exactly equal to
the energy difference E=E2-E1 between the two molecular energy levels, then the
molecule undergoes a transition from the lower energy level to the higher energy with the
absorption of energy (h). The spectrum thus obtained is called the absorption spectrum.

If the molecule falls from the E.S to G.S with the emission of photon of energy, h the
spectrum is called emission spectrum.

• The molecular spectra are governed by the selection rules which specify the changes in
the quantum nos. accompanying a particular transition.

• Selection rules are the backbone of spectroscopy and are obtained from the quantum
theory of interaction of radiation with matter.

For Diatomic molecule, H2, NO, CO, etc., the selection rule for a pure rotational transition is
J=±1 where J = rotational quantum no.. The selection rules for a pure vibrational transition
is v=±1 where v= vibrational quantum no.

• The spectral transition which obey a given selection rule are called allowed transitions
whereas those which violate selection rule are called forbidden transitions.

• Allowed transitions are more intense (strong ) than the forbidden transition which are
weak.

• Atomic spectra arise from the transition of an electron between the energy levels while
the molecular spectra arise from the three types of transitions viz., rotational, vibrational
& electronic transitions.

• The total energy of a molecule, according to Born-Oppenheimer approximation is given

• The translational energy is not quantized whereas all the other energies are quantized.

• Eele>>Evib>>Erot>>Etr

• Since Etr is negligibly small, we can write B.O.A as

• E=Erot+Evib+Eele
• The rotational spectra of a molecule are observed in the microwave; the vibrational
spectra in the IR region & the electronic spectra in the UV and visble region of the
Electromagnetic spectrum.

1. Microwave spectra: These spectra result from transitions between the rotational energy
levels of a gaseous molecule on the absorption of radiations falling in the microwave
region.

• These spectra are shown by molecules which possess a permanent diploe moment e.g,
HCl, CO, H2O vapour, NO, etc.

• Homonuclear Diatomic molecule such as H2, Cl2, etc., and the linear molecules such as
CO2, which do not possess a dipole moment, do not show microwave spectra. The
microwave region range from 1-100 cm-1.

2. Vibrational and Vibrational Rotational(Infrared) Spectra:

These spectra originate from transitions induced between the vibrational energy levels of
a molecule on the absorption of radiation belonging to the infrared region. IR spectra are
shown by molecule when vibrational motion is accompanied by a change in the dipole
moment of the molecule. These spectra occurs in the spectral range of 500-4000 cm-1.

3. Raman Spectra:

It relate to vibrational or rotational transition in molecules but in a different manner.

In this case , we measure the scattering and not the absorption of radiation.

An intense beam of monochromatic radiation in the visible region is allowed to fall on a

Most of the scattered light has the same frequency as the incident beam (Rayleigh
scattering). However, a small amount of light has the different frequencies than the
incident beam. This is called Raman scattering. The energy differences between these
weak lines and the main Rayleigh line correspond to vibrational or rotaional transitions in
the molecule under investigation. Raman spectra are observed in the visible region, viz
12,500-25,000 cm-1

3. Electronic spectra :

It arise from electronic transitions in a molecule by absorptions falling in the visible and
UV regions. & the electronic spectra in the UV (5,000-70,000 cm-1) and visble region of
the Electromagnetic spectrum (12,000-25,000 cm-1). Since electronic transitions in a
molecule are invariable , the electronic spectra on molecules are highly complex.
4. NMR & Nuclear Quadropole Resonance Spectra, NQR:

NMR spectra result from NQR result from the Transition between the nuclear spin
energy levels of a molecule in an applied magnetic field. arising from the interaction of
the unsymmetrical charge distribution in nuclei with the electric field gradients which
arise from the bonding and non-bonding electrons in the molecule. NMR and NQR
spectra span the radiofrequency regions viz., 5-100 MHz.

5. ESR or EPR :

Transition induced between the electron spin energy levels of a molecule in an applied
magnetic field. These spectra are exhibited by systems which contain odd (unpaired)
electrons such as free radicals & transition metal ions. Molecules a=such as nitric oxide
and oxygen and other paramagnetic systems also saw ESR spectra. These branch of
spectroscopy falls in the microwave region., viz., 2-9.6 GHz.