Rotational and Vibrational Levels

of Molecules

Lecture 23
www.physics.uoguelph.ca/~pgarrett/Teaching.html
Review of L-21
• Beer-Lambert law
− Cx − x
I = I 0e = I 0e
• Transmittance
I (λ )
T=
I 0 (λ )
• Absorbance
I 0 (λ )
A = log = 0.4343 x
I (λ )
• Extinction coefficient
= 0.4343





Rotations and vibrations
• We have examined electronic transitions in molecules
– But they can also rotate and vibrate
– ex. O2





Rotations and vibrations
• Become more complicated for more complex molecules
– ex. H2O rotational modes





Rotations and vibrations
• Become more complicated for more complex molecules
– ex. H2O vibrational modes





Vibrations
• Just like the electrons, molecular motion is governed by
quantum mechanics
– Energies due to rotation and vibration are quantized
• Molecular vibrations
– Chemical bond acts like a spring and can display SHM
– Have an effective spring constant k for the bond involved and
effective mass meff
– Angular frequency
k
=
meff
– Energy of vibration

Ev = (v + 1 2 ) = (v + 1 2 )hf
– ½ ω comes from quantum mechanics and represents
zero-point energy





Vibrations
• Vibrational energy

Ev = (v + 1 2 ) = (v + 1 2 )hf
• Vibrational quantum number v = 0,1,2,3,…
• The zero point energy ½ ω implies molecule never stops
vibrating, even when its in the v = 0 state!
– Zero point energy cannot be harvested or extracted
– Still exists at absolute zero
• All molecules are then in v = 0 state
• Energy levels are equally spaced with separation ω
• Obey selection rule ∆v = ±1 if no accompanying electronic
transition
– Otherwise can be anything





Molecular vibrations
• For diatomic molecule with mass M1 and M2, effective mass
meff can take the simple form M 1M 2
meff =
M1 + M 2
• Energy scale for molecular vibrations is much less than for
electronic excitations
• Excitation energies correspond to IR region of the spectrum
– Typical wavelengths are 2 – 50 µm = 2000 – 50000 nm for organic
molecules
• Vibrational levels are built on electronic states – each
electronic state will host the whole range of vibrational states





Vibrational excitation and de-excitation
.
. v
. Probability
3 distribution for
π electronic 2 which v state is
1 IR radiation populated
state n = 2 0 during the ∆n
visible visible transition
radiation radiation

.
. v At normal
.
π electronic 3 temperatures,
most of the
state n = 1 2
molecules will
1
0 be in the v = 0
IR radiation state
Fundamental IR transition





Molecular rotations
• In quantum mechanics, the rigid rotor has energy levels
2
EJ = J (J + 1)
2ℑ
where ℑ is the moment of inertia (PHY1080), J is the angular momentum,
J = 0,1,2,3,…
2
• The quantity is called the rotational parameter
2ℑ
• Moment of inertia, hence rotational parameter, can be different for each
rotation axis
• Excitation energies correspond to the microwave region
• Energy scale for rotations << vibrations
– Each vibrational level has rotational bands built on it
• Selection rule ∆J = ±1





Rotational levels
.
. J
. Two types of
3 transitions, J
vibrational 2 increasing, and J
state v = 1 1 decreasing, populated
0 during the ∆v transition
IR radiation

.
. J
vibrational
. At normal
3 temperatures,
state v = 1 2 molecules will have
1 a distribution
microwave 0 amongst the J states
radiation





Vibrational-rotational IR spectrum
• HCl

→3
2→
→4
3→
→2
1→
→5
4→
5→→6
6→→7

→8
7→

→9
8→

→10
9→

→11
10→

→12
11→





Energy levels
• Taking rotations, vibrations, and electronic excitation into account

E n ,v , J = E n + E v + E J
n 2h 2 2
E n ,v , J = + (v + 1 2 ) + J (J + 1)
2me 2
2ℑ
Ring molecule

• If the measuring instrument has very good resolution, it is possible to see

the discrete transitions
• Complex molecules may have many vibrational modes, rotational modes,
etc. The combination of these different modes leads to a “smearing” of
the discrete spectrum (temp. effects too) so that broad bumps appear
rather than discrete lines





Water absorption spectrum

IR Radiowave