The rotational spectra

of diatomic molecules

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 Key concepts in rotational spectroscopy

Rigid and non-rigid models of molecules

Center of mass
Moment of inertia
Discrete rotational energy levels
Spectral lines and their intensities
Applications of rotational spectroscopy:
isotope effect and bond length measurement

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Molecular models: simplifying reality

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 Type of rotors
• Rigid rotor • Non-rigid rotor

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Center of mass: static view

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Center of mass: dynamic view

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Center of mass of a diatomic molecule:
mathematical view

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Moment of inertia

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Moment of inertia of a diatomic
molecule: mathematical view

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Rotational energy levels of a rigid rotor
from quantum mechanics

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 Emission and absorption of
electromagnetic waves by a rigid
rotor

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Energy diagram of a rigid rotor

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 The rotational spectra of a rigid
rotor: selection rules
• Only a molecule with a
permanent electric dipole
moment may interact with
electromagnetic waves

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The microwave spectrum of CO: general
features of rotational spectra

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Intensity of spectral lines: the role of
temperature on population

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 Intensity of spectral lines: the role
of quantum degeneracy
• What is degeneracy? • When degeneracy
emerges?

Degeneracy emerges when a

physical quantity of a
system may be changed
without affecting the
energy of system

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 Angular momentum in classical and
quantum mechanics
• Classic version • Quantum version

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Quantum degeneracy associated to
angular momentum

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Degenerate energy levels of rigid rotor

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Intensity of spectral lines: The final outcome

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Isotope effect: The role of atomic masses

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 Non-rigid rotor
• The bond length is not
completely constant

• When J grows the bond

length also increases

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Energy levels and their spacing in non-
rigid rotor

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Comparison of rigid and non-rigid rotors

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 What one learns from rotational
spectra
• Precise measurement of bond length

• The ratio of isotopes masses

• The amount of non-rigidity of a bond

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 Let’s Consider the
rotational spectra of
polyatomic molecules in
next session

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