4.

The interaction of light with matter

The propagation of light through chemical materials is described by a

wave equation similar to the one that describes light travel in a vacuum (free
space). Again, using E as the electric field of light, v as the speed of light in a
material and z as its direction of propagation.
!2 1 ! 2E ! 2 E # 1 & ! 2 E # n2 & ! 2 E
E= 2 2 " =% ( = .
!z 2 c !t ! z 2 $ v2 ' ! t 2 %$ c 2 (' ! t 2
(Read the variation in the electric field with respect distance traveled is
proportional to its variation with respect to time.) The refractive index, n, (also
represented η) describes how matter affects light propagation: through the
electric permittivity, ε, and the magnetic permeability, µ.
! µ
n=
! 0 µ0
These properties describe how well a medium supports (permits the transmission
of) electric and magnetic fields, respectively. The terms ε0 and µ0 are reference
values: the permittivity and permeability of free space. Consequently, the
refractive index for a vacuum is unity. In chemical materials ε is always larger
than ε0, reflecting the interaction of the electric field of the incident beam with the
electrons of the material. During this interaction, the energy from the electric field
is transiently stored in the medium as the electrons in the material are
temporarily aligned with the field. This phenomenon is referred to as
polarization, P, in the sense that the charges of the medium are temporarily
separated. (This must not be confused with the polarization, which refers to the
orientation or behavior of the electric field.) This stored energy is re-radiated, but
the beam travel is slowed by interaction with the material. So, as the wave
equation above shows, the refractive index also is the ratio of the speed of light
in a vacuum, c, to the speed of light in the material, v.
c
n=
v
Energy in the beam is conserved as long as absorbance by the material is
negligible.
The wave equation states that the derivatives of light amplitude with
respect to time and distance are proportional, related through the velocity. The
only functions that satisfy this criterion are oscillations in time and space:
E(z,t) = E max cos (! t " kz + #o ); B(z,t) = Bmax cos (! t " kz + #o ) .
However, in this case, the wavevector k is ω/v= ω/(c/n)=2π/(λ/n), where c/n is the
speed of light in the material.
For all chemical materials, n is larger than 1 at all but X-ray wavelengths
due to the interaction of the material electrons and incident electric field. A
material that has ε≠εo and negligible magnetic interactions, i.e., µ=µ0, is called a
dielectric material. Materials that have tightly bound electrons, such as glasses

12
and other optical materials, are dielectrics. However, it can be more convenient
to use the electric susceptibility, χ, rather than the refractive index to describe
interactions of light with these materials because χ is zero in a vacuum, making it
more directly related to the extent of the physical interaction of light and the
material.
!
n2 = = 1+ "
!0
The electric susceptibility measures the ability of a material to become transiently
polarized, and the amount of polarization is proportional to χ and the electric field
strength:
P = (! " ! 0 ) E = ! 0 # E .
This relation holds as long as the electrons oscillate at the same frequency as
the electric field, i.e., as long as the intensity of the electric field is relatively low.
In nonlinear materials, i.e. those that have specific kinds of structural
anisotropies, intense laser beams (large electric fields) induce oscillations that
have higher frequency components. (More on this later.)
For chemists, the polarizability, α, is more familiar than the electric
susceptibility, χ. (Remember the discussion of the electrophilic addition of iodine
vs bromine in Organic? If not, ask.) The polarizability is linearly related to the
electric susceptibility:
! = "0 #
The refractive index is thus a measure of the polarizability of the material.
n2 = 1 + ! " 0
One of the important features of these parameters (that is not evident in the wave
equations) is that they are frequency (and wavelength) dependent. To see this,
we analyze the electric susceptibility by describing the chemical material as
through it were a collection of N electrons bound to N atomic nuclei per volume.
Since these charges are bound, they have a natural resonant frequency,
designated as ωo (remember ! 0 = k m ). Assuming a linear response to incident
electric fields, and that oscillations fade with time after their source is turned off,
the system acts as a damped harmonic oscillator. Solving this system (as you
will for homework) reveals that χ is given by
Ne2 1
!= .
( )
me" 0 # 0 $ # 2 + 2i%#
2

In this expression, the charge of an electron is e, the mass of the electron is me

and the damping coefficient is γ, which is the inverse of the lifetime of the
oscillator. The consequence of this physics is that the electric susceptibility
consists of two components. χ is a complex quantity because photon irradiation
induces two independent physical responses in the material: dispersion, the
wavelength dependent propagation of the beam through the material and
absorption, the transfer of the radiant energy to vibronic energy in the material.
Since the refractive index is a function of χ, it must also be a complex quantity:
n=nreal+inimag.

13
 2
nreal = 1 + ! real ; 2
nimag = ! imag

Figure 4.1: Dispersion & Absorption of EMR by dielectric

Plots of the real and imaginary parts of n as functions of frequency are shown in
Fig. 4.1. The real part of the refractive index, nreal, is what we normally call the
refractive index; tabulated values of the refractive index (often measured at 589
nm) refer to nreal. Far from resonance, nreal is a weak function of frequency. In the
vicinity of the resonance frequency, the refractive index behaves strangely: nreal
first increases quickly, then falls below unity, and eventually makes its way back
up toward unity. This behavior near resonance is called anomalous dispersion.
The imaginary part of the refractive index, nimag, is a very weak function of
frequency far from resonance. Near the resonance, the imaginary refractive
index increases sharply to a maximum then falls as the frequency exceeds the
resonance frequency. The shapes of these functions for nreal and nimag will
eventually be familiar if they aren’t already. The real part of the refractive index
matches the imaginary part of the generic solution, which is called a dispersion
function:
( x ! x0 ) .
((
y = imag a + i ( x ! x0 ) )
!1
)
" 2
a + ( x ! x0 )
2

The imaginary part of the refractive index has the same shape as the real part of
the generic solution which is a Lorentzian function:

(
y = real ( a + i ( x ! x0 )) " 2
!1
) a
a + ( x ! x0 )
2

Lorentzians are distinguished by the fact that their bandwidth is 2a. In

spectroscopy, the focus is resonances so, nimag is large but changes in nreal with
frequency are typically small enough to be ignored in the experimental design.
For example, the absorptivity of a typical dye is so high that a solution can be
very darkly colored yet its refractive index rarely exceeds 2. In optics, on the
other hand, the radiation is off-resonance so, nimag is negligible while nreal is used
to control beam direction through refraction (next Section).
A convenient alternative notation for the solution of the wave equation
describing light propagating in materials employs complex notation, using Euler’s
relation: eiθ=cosθ+isinθ.
E(z,t) = E0 exp #$i (! t " kz ) %&

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We could avoid imaginary numbers by using E(z,t)=(1/2)E0{exp[i(ωt-kz)]+ exp[-
i(ωt-kz)]}, which is the same as E(z,t)=E0cos(ωt-kz). However, derivatives of
trigonometric functions are much more cumbersome than those of exponents.
Besides, complex quantities are efficient for describing processes that are related
but distinct. The variable definitions are the same as listed in the first Section
(Nature of Light). By substituting k=ω/(c/n), the electric field is separated into two
components. The first is phase-shifted compared to the incident radiation in free
space and the second is attenuated:
( ( ) ) ( )
E ( z,t ) = E0 exp #i ! t " nreal + inimag ! z c % = E0 exp #$i (! t " nreal! z c ) %& exp "nimag! z c .
$ &
This equation shows that light in a medium of refractive index n oscillates at
frequency ω, but experiences a change in apparent velocity to v=c/n. The
change in velocity (and wavelength) can also be viewed as a phase-shift in
space by (nreal -1)ωz/c compared to the same beam traveling in a vacuum. This
equation also shows that the electric field exponentially decays as it travels in the
direction z by an amount that depends upon nimag.
Since detection encodes the electric field as the irradiance:
E ! $ c 2" 0 E # B dt % $ E & E dt ,
t t
substituting the EMR expression above into the irradiance integral yields
(
E = E 0 exp #$ ! 2nimag " c z %& )
This relates to something very familiar. Remember Beer's law, which states that -
log(T) = εbC, where T= E/E0. (Remember this ε is not permittivity.) If the path
length, b, is made to be a variable, i.e., b=z, and we convert from base 10 to
base e, then Beer’s law states E/E0=exp(-2.3εzC). Consequently, nimag is directly
related to the molar absorptivity.
There are circumstances in which the polarization deviates from the
simple proportionality to E described above. Intense beams propagating in non-
linear optics induce polarization that is approximated by a series expansion that
includes first order, second order, etc., electric susceptibilities. The sizes of the
higher order susceptibilities are much smaller.
P = ! 0 " (1) E + ! 0 " ( 2 ) E 2 + ...
What we have been calling the electric susceptibility is now represented by χ(1)
and the higher-order nonlinear susceptibilities are χ(n). (Note that this is not a
power, i.e., χ(2) is not χ2.) In the wave equation, the refractive index, n, now
includes the higher order susceptibilities, which changes the solution to the wave
equation. As an illustration, if the χ(2) term is significant, while χ(3) and the higher
terms are negligible, the wave equation (in one direction) becomes the following:
! 2 E # (1 + " (1) ) & ! 2 E # " (2) & ! 2 E 2
= + .
! z 2 %$ c 2 (' ! t 2 %$ c 2 (' ! t 2

The E2 term describes an oscillation at 2ω, twice the frequency of E (You can
figure this out using trigonometric identities for sin2θ and cos2θ, etc). The result is

15
that frequency-doubled light is generated. In practice, frequency doubling is very
valuable. It is commonly used to convert IR beams to visible, for example, to
convert the 1.064 µm Nd:YAG laser beam to 532 nm. Crystals that have large
second-order susceptibilities, e.g. potassium dihydrogen phosphate (KDP) and
lithium niobate (LiNbO3), are used, and the incoming laser beam is tightly
focused to maximize E. Second harmonic generation (SHG) increases with the
coherence length, lc, of the material, which is given by
!
lc = ,
4 ( n1 " n2 )
where n1 and n2 are the refractive indices of the material for the fundamental (ω)
and doubled (2ω) frequency, respectively. The efficiency of SHG is given by
3/2
"µ % ( 2 d 2 " 2lc %
2

eSHG = 2$ 0 ' $ ' E1

#! &
0 n12 n2 # ) &
where µ0 and ε0 are the permeability and permittivity of free space, respectively.
The non-linear optical coefficient of the material, d, is related to the second order
susceptibility, χ(2). E1 is the irradiance of the fundamental beam on the crystal.
There has been a considerable effort in materials science to create thin films
having large values of χ(2) (or d) because such a material could be used in optical
computing. One red light beam of E1 would switch another red light beam of E2
because the output would be the product E1⋅E2 with a frequency in the UV.
Optical switching would greatly increase the speed of computing for scientific
calculations and searching of databases, as well as telecommunications to
enable much faster graphical communications such as faster access to the files
on the world wide web and broad use of video telephones. There also has been
phenomenal growth in the development and application of nonlinear
spectroscopies that usually involve the interaction of more than one laser beam
with the analyte. Examples of nonlinear spectroscopies include multiphoton
absorption, nonlinear Raman scattering, harmonic and sum-frequency
generation. Many of these techniques have important advantages relative to
linear spectroscopies. For example, second harmonic and sum-frequency
generation measurements are surface specific.

16