18.4 The interaction of light and molecules.

Molecular spectroscopy

Classifications of electromagnetic radiation:

Spectral classification: X-ray, Ultraviolet, Visible, Infrared, Microwave, Radio

Spectroscopic classification

Electronic spectroscopy, Vibrational spectroscopy, Spin spectroscopy (Magnetic

resonance)

Absorption of light and color

Photochemistry: photosynthesis, vision, atmospheric, toxic, theraputic

Photochemistry: involves electronically excited states
The distance and size scales of the electromagnetic spectrum
Energy Scales: Why the visible region works for vision

Ultraviolet Region Infrared Region

Chemical Bonds of Chemical Bonds Energy
DNA and Proteins too low to make or break
Damaged chemical bonds.

400 nm 500 nm 700 nm

71.5 kcal/mol 57.2 kcal/mol 40.8 kcal/mol

Huge energies Tiny energies

Themal energies per photon.
per photon. at room temperature
ca 1 kcal/mole
X-Rays Microwaves
0.1 nm 1,000,000 nm
300,000 kcal/mol 0.03 kcal/mol
Photochemistry and spectroscopy both involve the absorption of photons to change a
structure

The configurations of electron, the vibrations of atoms, the orientation of spins

 As conjugation is extended, the wavelength of absorption increases



Energy gap decreases: Wavelength increases

beta Carotene
Photochemistry: the science of chemical reactions which occur from electronically excited
states of molecules

R + h *R Chemical reactions

*R is an electronically excited state

Some important photochemical events:

Photosynthesis (electron transfer)

Vision (cis-trans isomerization)

Atmospheric: ozone layer (dissociation)

 Energy Levels
UV Visible absorption spectroscopy involves transitions between
electronic energy levels

UV ~ 200-400nm
Vis ~ 400-750nm

For  < 200nm (absorption by oxygen in air is significant) – vacuum UV

 Energy Levels
Population of energy levels
 Absorption Spectroscopy
Population of energy levels

• Net absorption depends on the difference between the populations of the

energy levels

• The more populated the ground state, the more intense the net absorption
is

• Two factors that influence absorption are the energy level spacing and the
temperature
 II. Absorption Spectroscopy
Electron transition rules
• Energy is absorbed by transitions induced between different electronic
energy states of a molecule

• Transition occurs only if there is an induced dipole moment

• Resonance condition; the frequency of radiation must be equal to the

frequency of the dipole
DE = hf
where, DE = separation of energy states,
h = Planck’s constant, f = frequency

h=6.626x10-34 m2kg/s
 II. Absorption Spectroscopy
Absorption strength

• The transition probability from electronic state m to state n is given by:

2

  d  |  mn |

Where, mmn is the transition dipole moment and eu is molar extinction coefficient at
particular frequency, n
 II. Absorption Spectroscopy
B. Franck Condon principle
• The time for an electronic transition is: t=1/n =l/c ~ 10-15 s (at 420 nm)

• Franck Condon principle: electronic transitions occur so rapidly that during

the transition the nuclei are static

• Thus, all electronic transitions are vertical (internuclear distance doesn’t

change)
 II. Absorption Spectroscopy
B. Franck Condon principle

Energy

Internuclear distance
 Jablonski Diagram

Skoog, Hollar, Nieman, Principles of Instrumental Analysis, Saunders College

Publishing, Philadelphia, 1998.
 Absorption

Selection Rules:
DJ = 1
Dv = 1, 2, 3, …
DS = 0 (i.e. S  S, T  T)

Very Fast  10-14 – 10-15 sec.

Skoog, Hollar, Nieman, Principles of Instrumental Analysis, Saunders College

Publishing, Philadelphia, 1998.
 Vibrational Relaxation
• Excited molecule rapidly transfers excess
vibrational energy to the solvent / medium
through collisions.
• Molecule quickly relaxes into the ground
vibrational level in the excited electronic
level.
• Non-radiative process
• 10-11 – 10-10 sec.

Skoog, Hollar, Nieman, Principles of Instrumental Analysis, Saunders College

Publishing, Philadelphia, 1998.
 Internal Conversion
• Transfers into a lower energy electronic
state of the same multiplicity without
emission of a photon.
• Favored when there is an overlap of the
electronic states’ potential energy curves.
• Non-radiative process (minimal energy
change)
• ~10-12 s between excited electronic states.

Skoog, Hollar, Nieman, Principles of Instrumental Analysis, Saunders College

Publishing, Philadelphia, 1998.
 Fluorescence
• Radiative transition between electronic
states with the same multiplicity.
• Almost always a progression from the
ground vibrational level of the 1st excited
electronic state.
• 10-10 – 10-6 sec.
• Occurs at a lower energy than excitation.

Skoog, Hollar, Nieman, Principles of Instrumental Analysis, Saunders College

Publishing, Philadelphia, 1998.
 Phosphorescence
• Radiative transition between electronic states of different multiplicities.
• Much slower than fluorescence (10-4 – 104 s).
• Even lower energy than fluorescence.

www.wikipedia.org
 Time Scales of Processes

http://micro.magnet.fsu.edu/primer/techniques/fluorescence/fluorescenceintro.html
 Transitions between molecular
potential energy surfaces

Excited State
During an electronic transition
the complex absorbs energy molecular rotations
lower energy
electrons change orbital microwave radiation
the complex changes energy state

electron transitions
higher energy
visible and UV radiation
Ground State

Timescale : ≈10-15 sec

molecular vibrations
Timescale of geometry changes medium energy
(vibrations): ≈10-12 sec IR radiation
As a result, observe vertical (Franck-Condon) transitions
In other words, we assume that we only have to consider the electronic
portion of the ground- and excited-state wavefunctions to understand
these transitions: Born-Oppenheimer approximation
Potential Energy Surface Description of the
Ionization of Dihydrogen
18 H2+
17

Ionization Energy (eV) 16

15

H2

0 1 2
r (Å)
Much more on this next time!!