Chemistry 24b

Spring Quarter 2004

Instructor: Richard Roberts

Lecture 23 & 24

Interaction of Light with Matter

The interaction of light with matter can take many forms.
(1)

Absorption and Emission of Photons

Photons are annihilated or created.

absorption

E2

E2

E1

E1

emission

E2 E1 = h

E2 E1 = h

must satisfy Bohr relation

emission could be induced

or spontaneous

Figure 9-1

Most absorbing materials satisfy the Beer-Lambert Law.

I0

absorbing molecules

Figure 9-2

Chemistry 24b Lecture 23 & 24

I0 incident light intensity at frequency

If

I intensity of transmitted light at same frequency

C concentration of absorbers
molar extinction coefficient
l length of light path through the absorbers
then

log10

I0
= lC
I

Quantity log10
(2)

I0
= A is called the absorbance or sometimes optical density (OD).
I

Light Scattering

An isolated atom scatters light because the electric field of the incident light wave forces
the electrons in the atom to oscillate back and forth about their equilibrium position. By
the laws of electromagnetism, when a charge changes its velocity, it emits radiation.
Light is emitted uniformly in all directions in the plane to oscillation, but decreases in
amplitude as the viewing angle shifts away from that plane.

E*
v
E of incident
light v0

atom

oscillation
of e

Figure 9-3

y
E*s
v
E*s
x

scatte
red li
ght

Chemistry 24b Lecture 23 & 24

E*s

v
E*s

xy plane
scattering light

Figure 9-4

E*s =

e a sin
c2 r

where e = electron charge

a = acceleration of electron
c = velocity of light
r = distance from oscillator
= angle between axis of oscillation and plane
containing direction of propagation of scattered light
Intensity of scattered light E*s

Scattered light is not necessarily at the same frequency as incident light.

(a) Rayleigh Scattering

Scattered light is essentially at the same frequency as incident light.

Frequency shift due to
(i) Molecular motion Doppler Shift
(ii) Change in internal energy states of scattering molecule

n
n

m
i

Figure 9-5

inelastic scattering

Chemistry 24b Lecture 23 & 24

Inelastic scattering is important for gases, e.g., rotational Raman. In liquids, random
molecular motions broaden Rayleigh scattering.

Incident frequency
Liquid
Rayleigh scattering

Raman scattering
(Stokes line)

Raman scattering
(anti-Stokes)

Brillouin
scattering

0
Figure 9-6
(b) Brillouin Scattering

In addition, in liquids, two special scattered lines, the Brillouin lines, appear because of
coherent molecular motion in sound waves that propagate through the fluid.
(c) Raman Scattering

Stokes

anti-Stokes
Figure 9-7

vibrational levels

Chemistry 24b Lecture 23 & 24

Phenomena Related to Light Scattering

(a) Reflection Light scattered in the opposite direction of incident light.
(b) Refraction Light scattered in the forward direction combines with the incident

beam to give rise to the phenomenon of refraction. The physical effect of this
combination is to make the transmitted light appear as though it has travelled more
slowly through the sample than through a vacuum.
index of refraction = n =

velocity of light in vacuum

velocity of light in substance

(c) Diffraction Superposition of scattered waves from individual atoms or molecules

in the sample. If the sample is highly ordered, diffraction pattern periodicity in the
distribution of atoms and molecules in the sample can be used to deduce or infer the
relative positions of atoms in a sample.
Fluorescence and Phosphorescence

vibrational levels
S-T intersystem crossing
(radiationless transition)

S2
vibrational levels
S1

absorption
of photon

lowest
vibrational
state of
radiationless 12
lowest
transition ~ 10 sec
excited
singlet
(
heat) psec
fluorescence
9
10
10 to 10 S

lowest
triplet

phosphorescence
6
10 or longer

S0
allowed transition

Figure 9-8

forbidden transition

Chemistry 24b Lecture 23 & 24

Optical Rotation and Circular Dichroism

(a) Optical Rotation Chiral molecules can rotate the plane of plarization of plane-

polarized light as light passes through the sample.

(b) Circular Dichroism Chiral molecules will absorb right and left circularly polarized

light differentially.
The Electromagnetic Spectrum and Molecular Spectroscopy
Study Table 12-2, p. 530-531.