Rotational Spectroscopy
or
Microwave Spectroscopy
By
Dr.puspanjali Mishra
Asst.Prof. in Chemistry
PMEC, Berhampur
Electromagnetic Radiation
Rotational Spectroscopy or Microwave Spectroscopy
• Spectroscopy in the microwave region is concerned with the study of rotating
molecules.
• Only molecules that have a permanent dipole moment can absorb or emit
electromagnetic radiation in microwave region results in transition between the
rotational energy levels
𝒉𝒗
• Molecule > Rotational Transition → Rotational spectrum/Microwave spectrum
𝑴𝒊𝒄𝒓𝒐𝒘𝒂𝒗𝒆
• Microwave spectrum occurs in spectral range 1cm-1 to 100 cm-1.
• 1cm-1 = 100 m-1
Microwave Active and Microwave Inactive Molecules
• Microwave spectra are shown by the molecules which possess
permanent dipole moment. Ex: HCl, NO, CO, H2O etc.
• Microwave active molecules: HCl, NO, CO, H2O, NH3 etc.
• Homo nuclear diatomic molecules (H2, Cl2, N2) and linear polyatomic
molecule like CO2, Which do not possess permanent dipole moment and
do not absorb microwave radiation.
• Microwave inactive molecules: H2, Cl2, N2, CO2 etc.
• Will the molecules CCl4, CHCl3, and CH2Cl2 show pure rotational spectra?
• CCl4 has such high symmetry that it has zero net dipole moment and will
not exhibit pure rotational spectra.
• CHCl3 and CH2Cl2 will both exhibit pure rotation spectra with non zero
dipole moment.
Rigid Rotator: Diatomic Molecules
The simplest model of a rotating molecule is that of a rigid rotator.
For a diatomic molecule like HCl, There are 3 directions of rotations :
• A) About the bond axis, the moment of inertia is zero about the bond axis.IA=0
• B) End over end rotation in the plane of the paper, IB.
• C) End over end rotation at right angle to the plane, IC.
• IB= IC.
• Thus interaction can occur, energy can be absorbed or emitted and the rotation
gives rise to a spectrum.
• Let us consider a rotating diatomic molecule of bond length R, about its
centre of mass.
Let the masses of the atoms are m1 and m2 and
their distance from the centre of mass be r1 and r2
respectively.
By the definition of centre of mass,
m1r1 = m2r2 ------(1)
r1 + r2 = R ------(2)
Moment of inertia, I = m1r12 + m2r22 --------(3)
From eqn. 1 & 2, we get
r1 = R – r2, m1(R – r2) = m2r2,
m1R – m1r2 = m2r2 , or (m1+m2)r2 = m1R
m1R
or r2 = ---------(4)
(m1+m2)
m2R
Similarly r1 = -------(5)
(m1+m2)
Using eqns 4 and 5 in eqn 3, we have
m22 R2 m12 R2 m1m2(m1+m2) R2 m1m2R2
I = m1r12 + m2r22 = m1 (m1+m2)2 + m2 (m1+m2)2 = (m1+m2)2 = (m1+m2)
m1m2R2
I= = 𝜇R2 , I = 𝜇R2 ---------(6)
(m1+m2)
m1m2
where 𝜇 = -----------(7), 𝜇 = reduced mass of the molecule.
(m1+m2)
• Thus the diatomic molecule is equivalent to a single point mass 𝜇, at a fixed distance R
from the axis of rotation. Such a system is called a rigid rotator.
• The angular momentum L = I 𝜔, where 𝜔 = angular velocity.
• In quantum mechanics, the angular momentum is quantized.
ℎ
L= J(J + 1) ----------(8), where J= 0, 1, 2, 3, ---- = the rotational quantum number.
2𝜋
1 𝐿2 ℎ2 ℎ2
The kinetic energy EJ = I 𝜔2 = = J(J + 1) = J(J + 1) .
2 2𝐼 2∗4𝜋2𝐼 8𝜋2𝐼
ℎ2
The rotational energy = the kinetic energy = EJ = J(J + 1) -------------(9)
8𝜋2𝐼
In microwave region, spectra are generally expressed in wave number units.
EJ ℎ2 ℎ
EJ= h c 𝑣ഥ𝐽 or 𝑣ഥ𝐽 = = J(J + 1) = J(J + 1) = B J(J + 1)
ℎ𝑐 8𝜋2𝐼∗ℎ𝑐 8𝜋2𝐼𝑐
ℎ
𝑣ഥ𝐽 = J(J + 1) = B J J + 1 --------- (10),
8𝜋2𝐼𝑐
ℎ
Where B = ----------(11)
8𝜋2𝐼𝑐
B = The rotational constant in wave number units.
Rotational energy levels of a molecule:
𝑣ഥ𝐽 = B J J + 1
J=0, 𝑣ഥ𝐽 = 𝑣ഥ0 = 0, zero point rotational energy. 20B J=4
J=1, 𝑣ഥ𝐽 = 𝑣ഥ1 = 2 B,
J=2, 𝑣ഥ𝐽 = 𝑣ഥ2 = 6 B,
J=3, 𝑣ഥ𝐽 = 𝑣ഥ3 = 12 B, 12B J=3
J=4, 𝑣ഥ𝐽 = 𝑣ഥ4 = 20 B,
J=5, 𝑣ഥ𝐽 = 𝑣ഥ5 = 30 B,
6B J=2
J=6, 𝑣ഥ𝐽 = 𝑣ഥ6 = 42 B,
2B J=1
0 J=0
Selection Rule for Rotational Transitions:
For an allowed rotational transition from J to J’ , ∆J = J’- J = ±1 . Or J’ = J ±1
All other transitions are spectroscopically forbidden.
Transitions like 0→1, 1→2, 3→4, 3→2 are allowed.
where as transitions like 0→2, 1→3, 3→1 are not allowed. J→J+1
Rotational Energy Transitions ∆ J = J’- J = ±1 :
J=0, 𝑣ഥ = 0, 𝑣ҧ (J→J+1) = 𝑣ҧ J+1−𝑣ҧ J =2B(J+1)
0
8B
J=1, 𝑣ഥ1 = 2 B, 𝑣ҧ (0→1) = 𝑣ҧ 1−𝑣ҧ 0 =2B−0=2B
J=2, 𝑣ഥ2 = 6 B, 𝑣ҧ (1→2) = 𝑣ҧ 2−𝑣ҧ 1 =6B−2B= 4B 6B
J=3, 𝑣ഥ3 = 12 B, 𝑣ҧ (2→3) = 𝑣ҧ 3−𝑣ҧ 2 =12B−6B= 6B
4B
J=4, 𝑣ഥ4 = 20 B, 𝑣ҧ (3→4) = 𝑣ҧ 4−𝑣ҧ 3 =20B−12B=8B 2B
J=5, 𝑣ഥ5 = 30 B, 𝑣ҧ (4→5) = 𝑣ҧ 5−𝑣ҧ 4 =30B−20B=10B
J=6, 𝑣ഥ6 = 42 B 𝑣ҧ (5→6) = 𝑣ҧ 6−𝑣ҧ 5 =42B−30B=12B
Allowed rotational transitions:
8B
6B
4B
2B
Rotational Spectrum
• A number of equidistant spectral lines are obtained.
• The first spectral line occurs at 2B
• The difference between two
subsequent spectral lines = 2B
Q. Calculate the reduced mass of HCl molecule.
• Solution:
Q. Calculate the bond length of CO molecule, the rotational spectrum of
which has equidistant lines separated by 20 cm-1 .
• Solution:
The HF molecule has bond length r = 1.10 x 10-10 m. Calculate its
rotational constant in cm-1, Jules and Hz.
Effect of Isotopes
• Isotopes of an atom have different atomic masses.
• With different masses, the reduced masses will be different.
• As
Calculate the reduced mass of the following isotopic molecules: diatomic
molecules 1H35Cl, 2H35Cl, 1H37Cl. Predict the relative rotational constants.
