• When the Morse anharmonic potential is

used, the permitted vibration energy levels

are defined by the expression:

1 1
𝜀 = (𝜈 + ) − x (𝜈 + ) 𝜈
2 2

v = 0, 1, 2, …. vmax
xe = anharmonic constant

• The energy levels are no longer equally

spaced. The number of vibrational energy
levels are finite. Dissociation of the
chemical bond takes places for energies
larger than E .
The 1H35Cl molecule is quite well described by the Morse potential. Assuming
that the potential De does not change on deuteration, predict the dissociation
energies D0 1H35Cl and 2H35Cl.

1 1
E = ℎ𝑐 𝜈+ −x 𝜈+ 𝜈̅ Important information
2 2
D = 5.33 𝑒𝑉
D =D −E 𝜈̅ = 2989.7 cm
x 𝜈̅ = 52.05 cm
h = 6.62608 x 10-34 J s
c = 2.9979 x 108 m s-1
1 eV = 1.602177 x 10-19 J
 IR inactive molecules
• EM radiation can induce vibrational transitions only for vibration modes that induce
changes in the molecular dipole moment. Such vibrations are infrared active. The
stretching vibration in heteronuclear diatomic molecule is always infrared active.

• Conversely, such a vibration is infrared inactive for homonuclear diatomic molecules.

In other words, homonuclear diatomic molecules are transparent to infrared radiation.

• Infrared inactive sample means those specific vibrational motions do not absorb
infrared light. It does not mean that the molecule stops vibrating.

• The intensity of the signal in vibrational spectrum increase with the molecular dipole
moment.
 Selection rules
• Selection rules for vibrational spectroscopy: Δν=±1.

• According to the Boltzmann distribution, almost all

molecules populate the vibrational ground state (ν =
0) at room temperature (298 K or kT = 207 cm-1).

• According to the selection rules, only one transition

Absorbed Intensity
is allowed from the vibrational ground state to the
first excited state to the first vibrational excited state
(ν=1 ← v=0 or 1 ← 0).

Wavenumber (cm-1)
Calculate the relative number of Cl2 molecules in the ground and first vibrational state at
298 K and 500 K when 𝜈 = 559.7 cm and ΔE ⟵ = hc𝜈.
(h = 6.62608x10-34 J s, c = 2.9979x108 m s-1, kB = 1.38065x10-23 J K-1)
The wavenumber of the vibrational fundamental transition of 1H35Cl is 2990.95 cm-1.
Calculate the force constant of the bond.
(1 amu = 1.66054x10-27 kg, h = 6.62608x10-34 J s, c = 2.9979x108 m s-1)
The selection rule Δν = ±1 is derived assuming a parabolic curve for the potential
energy curve (harmonic oscillator approximation). When anharmonicity is
considered, the selection rule Δν = ±1 does not hold rigorously and in fact all values
of Δν are allowed.

This is confirmed by the presence of weak bands (overtones) in the absorption

spectrum corresponding to the transitions 2←0, 3←0, etc.

Absorbed Intensity
Wavenumber (cm-1)
1) ν=0 → ν=1; Δν=+1 ; fundamental with considerable intensity
2) ν=0 → ν=2; Δν=+2 ; first overtone with small intensity
3) ν=0 → ν=3; Δν=+3 ; second overtone with negligible intensity

From any two transitions we can calculate equilibrium vibration frequency,

anharmonic constant and the force constant.
ν=1 → ν=2 is very weak due to the very small number of molecules in the upper
energy state. If temperature is raised, the population of excited state may become
significant.

If this absorption were to occur, it will be found close to and at slightly lower
wavenumber than the fundamental. [ ]

These weeks bands are known as HOT BANDS.

Separation between two neighboring levels can be calculated.

This separation decreases with increasing ν and the dissociation limit is reached
when Δε→0. The maximum value of ν is given by νmax.
 Rotational Spectroscopy
• In rotational Spectroscopy, EM radiation in the microwave region of the spectrum
interacts with matter and induce rotational motion.

λ = 30 cm to 3 mm
ν = 1 GHz to 1000 GHz
 Rotational Spectroscopy
Features
- Applicable to molecules with dipolar moment.
- Sample is usually in gaseous phase

Advantages
- High resolution
- High sensitivity
- Nondestructive technique

Applications
- Accurate determination of geometric parameter such as bond lengths and bond angles.
- Study of planarity and non-planarity of molecules
- Determine electric properties of molecules (dipole moment)
- Qualitative and quantitative analysis of gaseous mixtures
 Moments of Inertia
• The rotational motion of a molecule can be accurately described when its moment of
inertia is known.

• The moment of inertia of a system is defined as:

I = ∑ mr

• I is the inertia of the system.

• It depends on the mass distribution of the system.

 Moments of Inertia
Rigid rotors can be classified as:

Linear Rotors: Ia = Ib, Ic = 0 CO, CO2

Spherical Rotors: Ia = Ib = Ic CH4, SF6

Symmetric Rotors: Ia = Ib ≠ Ic NH3

Asymmetric Rotors: Ia = Ib ≠ Ic H2O

 Rotational energy levels
• The quantum mechanical expression for rotational energy of a molecule depends on the
symmetry of the molecular structure.

• For linear rotors only one moment of inertia needs to be defined, and the corresponding
rotational energy is:

E = J(J + 1) = J(J + 1)hcB

𝜀 = 𝐵𝐽 𝐽 + 1

B = (Rotational constant in cm-1)

Rotational energies: when J=0, ε0=0; when J=1, ε1=2B; when J=2, ε2=6B,
when J=3, ε3=12B: when J=4, ε4=20B
Rotational energy levels
Rotational energies:

J=0 ε0=0

J=1 ε1=2B

J=2 ε2=6B,

J=3 ε3=12B

J=4 ε4=20B
Rotational energy levels
Rotational energies:

J=0→J=1; Δε=2B

J=1→J=2; Δε=4B

J=2→J=3; Δε=6B

J=3→J=4; Δε=8B
The rotational constant of 127I35Cl is 0.1142 cm-1. Calculate the bond length of the
molecule.

h
B = I = mr
8𝜋 cI
The rotational constant of 127I35Cl is 0.1142 cm-1. Calculate the bond length of the
molecule.

h
B = I = mr
8𝜋 cI
 Rotational Transitions
• EM radiation can induce Rotational transitions only in a molecule with a permanent
dipole moment.

• Hence, only a polar molecule can produce a rotational spectrum.

• Homonuclear diatomic molecules and molecules with spherical symmetry are not
directly observable with rotational spectroscopy.

• The intensity of the signal in a rotational spectrum increase with the molecular dipole
moment.

• According to selection rules, allowed transitions are defined by:

ΔJ = ±1
Rotational absorption lines from 1H35Cl gas were found at the following
wavenumbers. 83.32 cm-1, 104.13 cm-1, 124.73 cm-1, 145.37 cm-1, 165.9 cm-1,
186.23 cm-1, 206.60 cm-1, and 226.86 cm-1. Calculate the moment of inertia and the
bond length of the molecule.
h
B = I = mr
8𝜋 cI
Is the bond length in 1HCl the same as 2HCl? The wavenumbers of the J=1←0
rotational transition for 1HCl and 2HCl are 20.6764 cm-1 and 10.7840 cm-1,
respectively.