EE611 : Organic Electronics

Absorption and Emission : Stokes Shift

Introduction : The aim of this assignment is to provide a feel for electronic absorption
and emission spectra and the associated stokes shift. Figure 1 below shows a
configuration diagram (energy of the molecule as a function of generalized nuclear
coordinates) with ground state EO and next excited electronic state E1.

E1
3

E0

Figure 1
It may be recalled that associated with each electronic level, there are a number of
vibrational levels (0, 1,). Because the nuclei cannot react in the short interval during
which optical transition takes place, both absorption and emission are depicted as vertical
transitions in the above diagram. Assuming that the molecule is in ground state, the
absorption will take place from O vibrational state of EO to 0, 1, 2 vibrational levels of
the excited state E1. Thus the absorption spectra may show all these transitions. Let us
assume that the energy corresponding to S00 transition (from O vibrational state of EO to
0 vibrational state of E1) is EA and that vibrational levels in both ground and excited
state are spaced at E. The transition S0j then would correspond to an energy EA+j E.
In the absence of any broadening, the absorption spectra would show a series of equally
spaced lines as illustrated in Figure 2. The strength of each transition depends on the
square of the overlap integral
I 0 j = 0* j dQ

(1)

where 0 is the wavefunction associated with vibrational state O of EO and j with

vibrational state j of E1.

0.06
0.05

Intensity

0.04
0.03
0.02
0.01
0.00
0.0

0.5

1.0

1.5

2.0

Energy (eV)

Figure 2
In the presence of broadening, the absorption spectra may look as illustrated in Figure 3.

0.06
0.05

Intensity

0.04
0.03
0.02
0.01
0.00
0.0

0.5

1.0

1.5

2.0

Energy (eV)

Figure 3
If broadening is further increased, the spectra may look like as illustrated in Figure 4

0.06
0.06

0.05

0.05

Intensity

0.04

0.03
0.02
0.01

0.03
0.02
0.01

0.00

0.00

0.0

0.5

1.0

1.5

2.0

0.0

0.5

Energy (eV)

1.0

1.5

Energy (eV)

Figure 4

Figure 5

With more broadening the spectra would not show any vibrational features at all (Figure
5). Once the electrons are excited, they quickly loose excess vibrational energy and settle
down into the lowest vibrational state of the excited state. Emission then takes place from
the lowest vibrational state of the excited state to different vibrational levels of the
ground state. It is clear from Figure 1 that the energy corresponding to Sj0 transition
(from O vibrational state of E1 to j vibrational state of E0) will be EA-j E. This clearly
shows that the emission spectra would be displaced towards lower energy levels (or redshifted in terms of wavelength) as compared to absorption spectra. This is called the
Stokes shift which occurs due to vibrational loss in the excited state. A typical absorption
and emission spectra are illustrated below:
0.06
0.05
0.04

Intensity

Intensity

0.04

0.03
0.02
0.01
0.00
0.0

0.5

1.0

1.5

2.0

Energy (eV)

Step-by-Step Procedure

Figure 6

We will model the potential energy surface of EO and E1 as a perfect parabola in single
nuclear coordinate y. We will assume that the excited state parabola is displaced from

2.0

ground state parabola by yO which we will take as variable. We will also assume that EA,
the energy separation of O vibrational state of EO and 0 vibrational state of E1 is 2.5eV
and that vibrational levels are spaced at 0.2eV (the numbers are arbitrary). For simplicity,
we will consider five vibrational states in both ground and excited states. It is easy to
calculate then the energy levels corresponding to emission and absorption transitions. To
estimate the strength of each transition we will have to calculate the overlap integral. For
that we will require the wavefunctions for vibrational states associated with both ground
and excited state. A potential of the form of a parabola corresponds to simple harmonic
oscillator, whose first five wavefunctions are given below:
y2
)
2
y2
1 = A1 y exp( )
2

0 = A0 exp(

(2)
(3)

y2
)
2
y2
3 = A3 (3 y 2 y 3 ) exp( )
2

2 = A2 (1 2 y 2 ) exp(

4 = A4 (3 12 y 2 + 4 y 4 ) exp(

(4)
(5)
y2
)
2

(6)

The wavefunctions corresponding to excited state are similar except that y has to be
changed to y-yO.
(i)

Determine the normalization constant Ak as follows:

AK2

k2 dy = 1

(ii)

Determine the strength of each optical (absorption as well as emission)

transition by carrying out the overlap integral described by Eq. (1).

(iii)

Plot the absorption and emission spectra (as a function of energy) assuming
that each spectral line is broadened into a Gaussian form as described below:
g ( E ) = exp(

(E E p ) 2
2 2

where EP is the energy associated with transition and describes the

magnitude of broadening.
(iv)

Illustrate the impact of yO and on the spectra.

Show all your analysis, calculations and attach relevant graphs to explain your work.
You may use Matlab, C programming or other means to compute integrals. You may
also add other calculations that would provide further insights into the phenomenon
under discussion.
4