Absorption Spectrum of a

Conjugated Dye


Dye Characteristics
Absorption occurs in the visible region of
the spectrum
Absorption intensities are very high
Usually organic molecules
Absorption frequencies are dependent on
the length of the conjugated system
Characteristics of Spectra
Transition energy
Bohr frequency condition:
H = E
2
E
1

Transition intensity
Transition moment
(
x
)
mn
= <
n
| ex |
m
>
Transition length
(x)
mn
= <
n
| x |
m
>



Typical Dyes
CH
3
( CH == CH)
n
CH
3

Conjugation in Cyanine Dyes






Transition Strength
D
nm
= <
n
| x
2
+ y
2
+ z
2
|
m
>




} }

~ =
high
low
high
low
d
d
e N
hc
D
n
nm
=
=
=
=
= = c
= =
=
= c
t
) (
1
10 98 . 3 ) (
8
3
20
2 3
Where the dimensions of D are cm
2
and the frequency is
in wavenumbers. The above equation is for a solution.
A symmetric Gaussian-shaped band allows the integral to
be estimated by:
}
= h d ) 0645 . 1 ( ) (
max
c = = c
Where h is the half-width of the band at its half-height
(in wavenumbers).
The dye molecules conjugated system of length L may be
represented by the Particle in a Box model potential with
solution:
Where the absorption excites the molecule from the energy
state E
1
to the excited energy state E
2
. According to the Bohr
Frequency Condition then:
Where the quantum numbers for the two half-occupied
orbitals involved with the transition are n
2
and n
1
for the
excited and ground state half-occupied orbitals, respectively.
This gives a transition energy of:
There are N electrons in the system so now the energy is:
Spectrophotometer spectra are usually produced as a
function of wavelength so since:
We can write:
The number of carbon atoms in the box is p = N 3
which affords an easy expression for the conjugation
length, L, in terms of the bond length, l:
So the wavelength of the absorption may now be expressed as:
And with substitution of the appropriate values for the constants:
Different dyes have different end groups of different
polarizability, and this leads to the final expression:
Quantum Dots
Instrumentation for Spectroscopy
) sin sin ( | o = a n
Photomultiplier Tube
Experimental Procedure
Lambert-Beer Law

I
I I I - dI I I
Sample of concentration c and
cell of pathlength d
Double-beam Spectrophotometer
Safety
Dyes can be toxic and some have been
associated with carcinogenicity.
Wear gloves in handling the dyes and their
solutions.
Immediately wash any contact with the dyes
or their solutions with soap and water.
Prepare a 10 ml sample of your assigned dye(s)
with an approximate concentration of 1.0 x 10
-3
M
by dissolving 3-5 mg of the dye in methanol.
Some solutions may already be prepared.
Use the spectrophotometer to obtain a solution
spectrum over the visible range (400-800 nm).
You may need to dilute the solution to insure that
the absorbance reading at the maximum wave-
length does not exceed 1.0 (10% transmittance).
At high concentrations of dye, dimerization may
occur which could alter the spectrum. For
sufficiently dilute solutions, dimerization does not
contribute to the spectrum.

Calculations
Plot spectra and decompose bands to obtain the peak
wavelength of absorption for each dye.
Using the appropriate equation, calculate the peak
wavelength of absorption for each dye.
1. Using the longest
max
calculate E
exp
for each dye and the
95% confidence limits. (Note: The 95% confidence limits of

max
may be taken as 1 nm.)
2. Use PIB equation to calculate E
theo
for each compound.
Compare the result to the experimental value.
3. For each set of dyes use an iterative method to calculate the
best-fit. Recalculate E
theo
for each dye, and compare the
results to the experimental values.


Choose the best value of ( how can you
use a least squares fit of the data?).
Use the Hckel Approximation to calculate
the best value of the exchange integral for
the dye series. Again, a regression analysis
should be considered.
The sum should be minimized for

obtaining the best-fit in a regression analysis.