Professional Documents
Culture Documents
Interaction of Light With Matter
Interaction of Light With Matter
Lecture 23 & 24
absorption
E2
E2
E1
E1
emission
E2 E1 = h
E2 E1 = h
Figure 9-1
I0
absorbing molecules
Figure 9-2
If
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
E*s
v
E*s
xy plane
scattering light
Figure 9-4
E*s =
e a sin
c2 r
n
n
m
i
Figure 9-5
inelastic scattering
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
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 =
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
light differentially.
The Electromagnetic Spectrum and Molecular Spectroscopy
Study Table 12-2, p. 530-531.