Rotational and Vibrational Levels of Molecules

Lecture 23 www.physics.uoguelph.ca/~pgarrett/Teaching.html

Review of L-21
Beer-Lambert law

I = I 0e
Transmittance

Cx

= I 0e

I ( ) T= I 0 ( )
I 0 ( ) = 0.4343 x A = log I ( )

Absorbance

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

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 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 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 m = 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 3 2 1 IR radiation 0
visible radiation

electronic state n = 2
visible radiation
. . .

Probability distribution for which v state is populated during the n transition

v 3 2 1 0

electronic state n = 1
IR radiation

Fundamental IR transition

 

At normal temperatures, most of the molecules will be in the v = 0 state

Molecular rotations
In quantum mechanics, the rigid rotor has energy levels

EJ =
2

where is the moment of inertia (PHY1080), J is the angular momentum, J = 0,1,2,3, The quantity

J (J + 1)

is called the rotational parameter

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 3 2 1 0

vibrational state v = 1
IR radiation

Two types of transitions, J increasing, and J decreasing, populated during the v transition

vibrational state v = 1
microwave radiation

. . .

J 3 2 1 0

At normal temperatures, molecules will have a distribution amongst the J states

Vibrational-rotational IR spectrum
HCl

23 12

34 45 56 67 78 89 910 1011 1112

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

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

J (J + 1)

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