Daniel Noteboom

Chem 155 AB Lab Report #5

Introduction: Spectroscopy is used to provide important information about the
electron energy levels in atoms, molecules, and solids so that the properties can be
better understood. A spectrometer can be used to measured absorption or emission
spectrum by reflecting different wavelengths at different angles and then recording
the amount of wavelengths with a one dimensional camera. The different angles
that the wavelengths are reflected depends on the grating constant. The grating
constant is the amount of slits/mm and can be measured if the wavelength of the
light entering is known and the constructive interference points are measured. Each
wavelength that enters the slits will constructively interfere at different parts of the
camera. If the wavelength is converted to energy using the formula Energy =
1240nm*ev/wavelength then the peaks show the energy emission or absorption of
the electrons. In this lab quantum dots, nanometer sized crystals of CdSe, and the
organic molecule 1,8 diphenyl 1,8 or octatetraene were analyzed using
spectroscopy. The absorbance at particular wavelengths is absorbed by taking
log(particles that escape/particles hitting the samples). Some assumptions need to
be made to determine the size of the particles based on the data. In this lab, the
assumption was that the electrons on the quantum dots and octatetraene behaved
like a particle in a box. For the quantum dots an four- part approximate equation
involving Egap, the effective mass of the electron, the hole left by the electron that
behaves like a real particle and the coulomb potential was used to determine the
radius of the quantum dots. For the octatetraene the particle in the box model can
be used to calculate the appropriate energy of the electron transition using the
Schrodinger equation results of Energy = n^2*h^2/(8*m*l^2) where m is the mass
of the electron, L is the length of the box, and n is the quantum number
corresponding to energy level. The size range of the quantum dots can also be
determined by analyzing the width of the peak at half its maximum. If the quantum
dots were all the same size then the peak width should be infinitely small at the
exact wavelength because only a particular energy value can be emitted by an
exact wavelength. Finally, the difference in absorption and emission peaks in the
quantum dots, which corresponds to varying levels of energy emitted and absorbed,
was analyzed to better understand the behavior of electrons in the quantum dots.
Experimental Methods:
1. The distance between the laser and the chalkboard was measured as L, as
well as the distance between the visible lines of order 0 and 1, D, for the
laser/grating set up.
2. Cyclohexane was used as a reference to diphenyl octatetraene to measure
the absorption and emission spectra of diphenyl octatetraene. The lowest
peak energy of each was measured as well as the integration time,
averages ,and boxcar settings. The emission was observed after UV light was
shined on the sample.
3. Step 2 was repeated for the blue, white, orange, green, yellow, and red
quantum dot samples
Results:

Daniel Noteboom
Chem 155 AB Lab Report #5

Emission vs Energy
Blue
White
Orange
Absorbance

Green
Yellow
Red
1.5 2 2.5 3 3.5 4 4.5
Energy(ev)

Figure1: A plot of the quantum dot

absorption vs. energy of the
wavelength for the
photoluminescence. The white
quantum dot peak is off the screen
because better data was obtained
(more particles of this wavelength
were absorbed). The peak at 3.5ev is
the noise due to the UV light and is
Lowest
Absorption
ignored. The data for yellow
was
not
Quantum Dot
Energy(
ev)
Blue
2.72
White

2.45

Orange

2.33

Green

2.2

Yellow

2.1

Red

Radius(
m)
1.80E09
2.10E09
2.28E09
2.55E09
2.84E09
3.27E09

Daniel Noteboom
Chem 155 AB Lab Report #5
Table
1:The
lowest
absorption
peaks of
Figure 2: A plot
of the
quantum
dots
absorption
the
quantum
dots
and
the
vs energy of the quantum dots. The data for blue
corresponding
of the
and green are highly
affected
by noise and
should
0.6energies
wavelengths.
The
approximate
equation
be shifted down.
The reference
was
probably not
0.4
for the
discussed in
calibrated correctly
forCdSe
thesenanoparticles
quantum dots.
the
introduction
was
used
to
calculate
Absorbance

Absorbance vs Energy
Blue
White
Orange
Green

0.2

0
1.5 1.8 2.1 2.4 2.7

Yellow
Red

Energy(ev)

Photoluminescence vs. Energy-Octatetraene

40
30
Absorbance

20
10
0
-10

Energy(ev)

Table 2: The energy of highest

peaks of the
photoluminescence emission
Figure 3: The photoluminescence
spectrum
for the
data corresponds
to the lowest
organic molecule Octatetraene
absorption peaks and was
recorded for each quantum dot.

Highest Emission
Quantu
Energy(
m Dot
ev)
Blue
2.55
White
2.37
Orange
2.267
Green
2.159
Yellow
2.06
Red
1.94

Daniel Noteboom
Chem 155 AB Lab Report #5

Absorbance vs. Energy- Octatetraene

2
1.5
Absorbance

1
0.5
0
2.82.9 3 3.13.2 3.33.4 3.53.6 3.73.8 3.9 4
Energy(ev)

Figure 4: The absorbance

spectrum for the organic
molecule Octatetraene.

Absorption Peak Energy vs Radius

3.50E-09
3.27E-09
3.00E-09
Radius(m)

2.84E-09
2.55E-09

2.50E-09

2.28E-09
2.10E-09

2.00E-09

1.80E-09
1.50E-09
1.5

1.7

1.9

2.1

2.3

Energy(ev)

2.5

2.7

2.9

Daniel Noteboom
Chem 155 AB Lab Report #5

Figure 5: The radius of the quantum dots that was

calculated using the approximate equation discussed in
the introduction
Grating Constant = 1.4810^5 lines/mm
Calculated Energy Difference of Lowest Absorption of octatetraene: 2.73 ev
Actual Energy Difference: 3.144ev
Wavelength of Energy Difference between Octatetraene Peaks: 7045 nm-infrared
and molecular vibrations
Full Width at Half Maximum for smallest quantum dot: 1.7810^-9 to 2.1110^-9
Discussion: To understand how the different wavelengths are diffracted at different
angles the diffraction constant was measured. For the wavelengths of light to
constructively interfere, the equation n*wavelength = d*sin must be met.
Constructive interference is when the corresponding peaks match up exactly so that
the absorbance of all the waves is much higher than one wave by itself. The angle
is approximated by calculated tan =D(distance between zero order and first order
light)/L(distance between laser and the chalkboard). N, the difference in order, is 1.
The angle is found to be 1.204 radians, and the wavelength of the laser is given as
632.8 nm. The grating constant is calculated by dividing 10^-3 by d which is
1.48*10^5 slits/mm. Different sized wavelengths will constructively interfere at
different usable points giving the same grating constant. The peaks observed on the
graphs are the corresponding wavelengths constructively interfere to produce a
higher absorbance.
Now that the underlying concept of spectroscopy has been laid out, the
quantum dots and octatetraene can be analyzed. In figure 4 the lowest peak of
octatetraene , 3.144 ev is very close to the energy calculated using the Schrodinger
equation n^2*h^2/(8*m*l^2). On the graph, 3.144 ev corresponds to the lowest
energy wavelength that was absorbed at significant quantities. This lowest energy
peak is the jump from the highest occupied energy level to the lowest unoccupied
energy level. In the Schrodinger equation The n values are a jump from n=4 to n=5
because each double bond has two delocalized electrons that are assumed to act
like particles in the box. The energy levels from 1 to 4 are each filled by two
electrons in this box of length 1.39 angstroms/bond * 8 bonds = 11.12 angstroms.

Daniel Noteboom
Chem 155 AB Lab Report #5
Since the electrons interact somewhat with each other and the molecule the
calculated Schrodinger equation for energy is only approximate.
In figure 4, the difference between each of the three peaks of the
octatetraene is about .176ev which corresponds to a wavelength of 7045.45
nanometers. This wavelength is on a scale of 10^-6 meters, the length of infrared
radiation or the vibrations of molecules. In this case the molecule is vibrating and
able to absorb higher energy wavelengths. In the quantum dots samples the lowest
peaks from the absorption, figure 1, correspond to the highest peaks in the
emission, figure 2. The results are recored in tables 1 and 2. The quantum dots are
not excited to the lowest energy of the excited state but a higher energy of the
excited state. After the electron is excited it falls to the ground level of the excited
state and the largest emission is from the ground state of the 1 st excited state to the
ground state of the ground state. This peak corresponds to the lowest absorption
value.
Some error occurred in figure 2. The blue and green absorbance data was
probably not calibrated directly so there is a lot of background noise but the peaks
can still be measured at about 2.7 ev for blue and 2.2 ev for green. In figure 1, there
is a lot of noise from the UV lamp at 3.5 ev and the white peak is much higher than
the other colors. The variations in the UV lamp noise at 3.5 ev shows that the UV
lamp was positioned differently for different quantum dots which led to some
variation of the size of the peaks. The peak of white is off the screen because the
absorption was around 200. The yellow peak is not observed because the data was
not recorded correctly but a peak was still observed during the lab and is used in
table 2 . There is also some noise in figure 1 around 3 ev. Since the peaks look
roughly the same for all the colors, another error occurred and these peaks were
also ignored.
The absorption peak energy from figure 1 was related to the radius size in
figure 5 using the four-part CdSe equation discussed in the introduction. As the
energy is lowered the radius goes down exponentially because the energy is
proportional to 1/radius^2 in the equation. The quantum dots that absorb smaller
wavelengths of higher energy, have smaller radiuses.
Since the quantum dots were not all exactly the same size the peaks have a
fairly wide range. The range can be approximated by taking the full width at half
maximum or FWHM, the peak at half its height on both sides of the peak. For the
smallest quantum dot, blue, this is a range from 2.4-2.63 ev or 471.48nm-508nm in
figure 1. In this calculation the peak was assumed to be at about an emission of 7.2
since the peak actually drops down to about 0 absorbance if all the noise is
removed. One final analysis is observed by noticing in table 1 and 2 that the lowest
absorption peaks are higher than the highest emission peaks. For example, blues
highest emission is 2.55ev, .17ev lower than the highest absorption. This shift is
called the stokes shift and is due to the fact that the excited molecules cannot be
excited directly to the ground state. The highest emission is fall from the ground
state of the excited state to the ground state of the ground state, a smaller fall than
the rise from the ground state of the ground state to a higher level than the ground
state of the excited state. The molecules emit energy as they fall to the ground
state of the excited state and some of this noise is below 1.5ev and is too small to
see in figures 1 and 2.
Conclusion: The lowest absorption peaks correspond to the highest emission peaks
with a slight shift called the Stokes Shift due to the fact that molecules cannot be

Daniel Noteboom
Chem 155 AB Lab Report #5
excited to the ground state of an excited state. The radius for the quantum dots was
found to decay proportional to 1/radius^2 because of the terms in the four part
equation involving the coulomb potential, E-gap, the effective mass of the electron,
and the hole the electron leaves. The particle in a box model is a decent estimator
for some electrons that are delocalized, such as the double bonds in the
octatetraene . The energy difference in the octatetraene peaks corresponds to the
vibrations of the molecule. The FWHM was used to establish a range of about 30nm
for the blue, the smallest quantum dot. To understand how the different
wavelengths are being reflected at different angles, the grating constant was
measured to show that different wavelengths will constructively interfere at
different ponts.