Spectroscopy/Rotational spectroscopy

A molecule can store energy in its tumbling motion.

Subject classification : this is a
This is only relevant in the gas phase where molecules are in continual chemistry resource.
motion and are free to rotate unhindered.
Rotational motion at the molecular level is quantized in accordance with Type classification : this is a
quantum mechanical theory. lesson resource.
Transitions between discrete rotational energy levels give rise to the
rotational spectrum of the molecule (microwave spectroscopy).
We will study:

classical rotational motion, angular momentum, rotational inertia

quantum mechanical energy levels
selection rules and microwave (rotational) spectroscopy
the extension to polyatomic molecules

Classical rotational motion

Rotational energy is kinetic energy associated with a tumbling motion.

Consider a particle with massm, rotating with angular velocityω, at a distance R from a given axis.

This particle has angular momentumJ

|J| = I ω where |J| is the magnitude of the angular momentum vector
, and I is the moment of inertia (the rotational
equivalent of mass).

Where do we use rotational spectroscopy? The 2.45 GHz frequency used by microwave ovens is the most ideal one for causing
water molecules to rotate at their fastest possible rate. There is also the added bonus that this frequency is not used for
communication, so microwave ovens do not interfere with cell phones, wireless internet, televisions and so on.

Diatomic molecules: the rigid rotor

Remember that a molecule does not distort under rotation.

R = r1 + r2 (Eq. 1)
The axis passes through the centre of mass (C):
 (Eq. 2)

Moment of inertia:

(Eq. 3)

Using equations 1, 2 and 3:

μ is the reduced mass.

Example: For 1H35Cl - (Remember that u = atomic mass unit = 1.661x10-27 kg)

Rotational energy levels

Classical:

Quantum mechanical: solve the Schrödinger equation for the rigid diatomic rotor
.

EJ is measured in Joules
J is the rotational quantum number (= 0, 1, 2, ...)
Converted to wavenumbers: Rotational constant:

The units of εJ and B = cm-1

Below are the rotational energy levels for diazenylium, N2H+.

N2H+
J = 0 → εJ = 0 0
J = 1 → εJ = 2B cm-1 ≈3 cm-1
J = 2 → εJ = 6B cm-1 ≈10 cm-1

Important points to notice:

The energy of the ground state J( = 0) is zero - because the molecule is not rotating.
As J increases, the molecules rotate more and more quickly - as a result, the energy levels are more widely spaced
apart.
 The energy level separations are compatible with the microwave region of the
EM spectrum.
But what about spectroscopic transitions between energy levels? And what about the
selection rules for microwave spectroscopy?

Gross selection rule

Gross Selection Rule: The requirement for a permanent dipole.

For example, take a rotating HCl molecule. The fluctuation in its dipole component has an identical form to the fluctuation in the
electric field of EM radiation (see the electromagnetic wave inLesson 1).

As a result, the electric field of the EM wave exerts a torque on the dipole of the HCl molecule.

This means that energy can be absorbed or emitted, giving rise to a rotational spectrum.

Gross Selection Rule: molecules with permanent dipoles are microwave active (the molecule must be polar), e.g.
heteronuclear diatomics - HCl, CO, NO, etc.

Homonuclear diatomics are microwave inactive (e.g. O

2, N2, etc.)

In other words, a dipole must be present in the molecule for you to get a rotational spectrum.

Transitions between energy levels

Specific Selection Rule: During a transition, the rotational quantum number must change by 1 unit only, i.e.
ΔJ = ±1 (angular momentum is conserved)
 In other words, only transitions between neighboring energy levels are possible.

Below is an example rotational spectrum.

The top part shows the rotational energy levels, εJ. The bottom part shows the microwave spectrum as observed from an experiment.

Each absorption (red arrow) complies with ΔJ = +1.

As a result of the equations in the box above, you get a series of spectral lines, each separated by 2B.

For CO, Δε = 3.86 cm-1. For HCl, Δε = 21.18 cm-1.

You'd get the same values for emission spectroscopy, except ΔJ = -1.

After obtaining a microwave spectrum from experiment, you measure nexp in cm-1. (The distance between spectral lines is Δnexp).
From this you can work the rotational constant B, because Δvexp (this is the intensity of each spectral line) = 2B. Using the formulae
in the green boxes further up this page you can work out B and I. Now you can calculate molecular properties (such as R, μ) to a high
degree of accuracy.
Rotational energy level population
Note that the most intense band is not the first line in the spectrum. Why?

Remember the 3 factors fromLesson 1:

1. Amount of sample
2. Population of energy states
3. Selection rules
We need to consider number 2 - the Boltzmann distribution AND degeneracy
.

Nf and Ni are the population of molecules in energy levels ef and ei with degeneracy gfand gI.

From quantum mechanics, the degeneracy of eacheJ level = 2J + 1

J=0 1 (non-degenerate)
J=1 3 (3-fold degenerate)
J=2 5 (5-fold degenerate)
J=3 7 (7-fold degenerate)

Population of excited state relative to ground state:

Initial state: J = 0 ei = e0 = 0 gi = g0 = 1
Final state: J ef = eJ = BJ(J + 1) gf = (2J+1)
Δε = εJ - ε0 = BJ(J + 1) →

Example for J = 1 (at T = 300 K):

B = 2 cm-1 Nf/Ni = 2.94

B = 10 cm-1 Nf/Ni = 2.70
The population of theJ = 1 level decreases as the energy level separation (i.e. 2B) increases.

Degeneracy (the pre-exponential term) moves the maximum population away from J = 0. You can use calculus to determine the most

populated level - the maximum which occurs when .

For example, at 300K,B = 5 cm-1 → kBT = 208.5 cm-1 → Jmax = 4 (which corresponds to the 4→5 transition).

Non-rigid rotor
Gray text is additional information provided for further reading only
. This content will not be tested.

We have assumed so far that the bond length remains fixed during rotation of the molecule - this is the rigid rotor model. However, as
the molecule rotates the atoms are subject tocentrifugal forces which stretch the bonds - this is the non-rigid rotor model.

Hooke's law states for an elastic bond:

F = restoring force (N)

r = bond length; req = equilibrium bond length (m)
k = force constant (Nm-1)
c = vibrational frequency (cm-1)
m = reduced mass (kg)
Non-rigid rotor model for diatomic molecules:

Non-rigid rotor model for diatomic molecules Centrifugal distortion coefficient

The first term is the rigid rotor model, and the second term is a correction for the centrifugal distortion. It is
important to consider this for high values of J.

Centrifugal distortion leads to lowering of the given energy level (at high J). Consequently, spectral lines cluster together at high J
and are no longer equally spaced.

Polyatomic molecules
The majority of molecules are not diatomic - they can possess rotation around more than one axis.

The classical expression for energy of a body rotating about axis a is

With similar expressions for the other axes, it follows that:

Polyatomic molecules are categorised according to their moments of inertia about 3 perpendicular axes:

Linear - one moment of inertia equals zero:Ia = Ib, Ic = 0. Molecules include CO2, OCS, C2H2.
Spherical rotor - three equal moments of inertia:Ia = Ib = Ic. Molecules include CH4, SiH4, SF6.
 Symmetric rotor - two equal moments of inertia:Ia = Ib ≠ Ic. Molecules include NH3, CH3Cl, CH3CN.
Asymmetric rotor - three different moments of inertia: Ia ≠ Ib ≠ Ic. Molecules include H2O, CH3OH, H2CO.

Calculation of B: Example
Calculate the value of the rotational constant B for a molecule of carbon monoxide. The bond length (R) of CO
is 0.113 nm.

Solutions

Step 1: Calculate the reduced mass using equation .

Step 2: Calculate the moment of inertia using equation .

Step 3: Calculate the rotational constant using equation .

Notice that a low m and a low R give a high B.

Lesson 3. Vibrational Spectroscopy

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