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Rotational and Vibrational Levels of Molecules: WWW - Physics.uoguelph - Ca/ Pgarrett/teaching - HTML
Rotational and Vibrational Levels of Molecules: WWW - Physics.uoguelph - Ca/ Pgarrett/teaching - HTML
Rotational and Vibrational Levels of Molecules: WWW - Physics.uoguelph - Ca/ Pgarrett/teaching - HTML
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
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
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
v 3 2 1 IR radiation 0
visible radiation
electronic state n = 2
visible radiation
. . .
v 3 2 1 0
electronic state n = 1
IR radiation
Fundamental IR transition
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)
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
Vibrational-rotational IR spectrum
HCl
23 12
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
IR
Radiowave