Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy
Introduction
Spectroscopy is a technique which uses the diffraction of light waves to measure the energy
transitions of electrons between different quantum mechanical states. In this experiment, we
apply this technique to measure the difference in energy levelsrepresented by principle
quantum number (n) levels--in alkene molecules and quantum dot particles. Analysis of these
real world experimental measurements allow a comparison with Schredingers equation and
particle-in-a-box calculations, allowing us to evaluate how well these models apply to
experimentally obtained data.
Absorption and photoluminescence are each processes related to spectroscopy. When light is
shined on a particle, photons excite electrons from one energy state to a higher one through the
process of absorption. Upon returning from their excited state to the ground state, the electrons
emit photons, demonstrating the process of photoluminescence. A spectrometer is used to
measure the absorption and light emission (photoluminescence) spectra of a substance.
Absorption spectra measure absorbance as a function of wavelength. The measurement of

absorbance (A) is given by the Beer-Lambert Law, = log ( ) = , where I0 is the intensity
0

of the incoming light wave and I is the intensity of the light transmitted. The log of their ratio

(Transmittance = ) is equal to absorbance. In Beers Law, gives the molar absorption

0

coefficient (M-1 cm-1), l is path length (cm), and C is concentration (M). Photoluminescence
spectra measure the intensity of the light emitted by excited electrons returning to lower energy
levels as a function of the wavelengths of photons released.
Spectroscopy relies on the mechanics of diffraction in order to measure intensities of light
emitted or absorbed. A diffraction grating, which is included in a spectrometer device, diffracts
incoming light waves at different angles depending on the their wavelengths. The number of
photons of varying wavelengths can then be measured. The mechanics of diffraction are
described by the equation: = =

. The interference of the waves creates a pattern:

points of light are created by constructive interference. nn being an integer and being
wavelength--indicates that a whole number of wavelengths must be traveled by adjacent waves
to result in constructive interference. The
distance between slits in the diffraction grating is
D
given by d. is the angle between the points

created by constructive interference, and D the

L
distance between these points, while L is the
distance between the diffraction grating and the
Figure 1: Schematic of diffraction grating
screen onto which the diffracted waves are projected.

Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy
The particle-in-a-box model provides a useful tool for analyzing our absorption and
photoluminescence spectra. A particle in a one-dimensional box gives the simplest form of
Schredingers equation. A 1-D box is defined such that the potential inside the box is 0, giving
the electron in the box freedom of movement within the box; but potential outside the box is
infinite, resulting in the confinement of the electron(s) to the box. For a 1-D box, Schredingers
2 2

Equation gives: = 82, where h is Plancks constant, n is the principle quantum number
associated with the state of the electron, m is the mass of the electron, and L is the length of the
box. Therefore, the change in energy between two quantum states for a 1-D box is: , =
2
82

(2 2 ) = =

. The energy of a transition between two such states is equal to the

energy of the photon released, h, which can also be represented by

due to the relationship

c = . As can be deduced from the equation, there is a correlation between the length of the box
and the amount of energy of the electron. As the length of a 1-D box decreases, the energy
increases, and there are more nodes in the wavefunction of the electron. An electron, whether in
a box or a molecule is described by its wavefunction () which offers information about its
amplitude and quantum properties. The square of the wavefunction gives the probability density
of an finding an electron in a particular section of the box. Since the total probability of finding
the electron somewhere in the box must be 1 so that all possible locations are accounted for, the
wavefunction is said to be normalized. In terms of application to real world situations, the
particle-in-a-box model is an approximation. The correlation between box length, energy, and
nodes extends to experimental evidence in that box length corresponds to the size of the orbital
of an electron or to the area about which it is delocalized. According to the Born-Oppenheimer
approximation, the nuclei in a molecule are fixed and electrons move rapidly around them due to
the much greater mass of the nuclei, which parallels the fixed ends of a 1-D box. It is notable,
however, that while the particle-in-a-box model assumes that electrons do not interact with each
other, experimental analysis must take into account the repulsion between electrons and other
Coulomb forces which influence electron movement in and geometry of molecules,
demonstrating a shortcoming of such approximations.
Our experiment will measure the absorption and photoluminescence spectra of both a set of
linear diphenyl alkenes and a set of nanocrystal quantum dots.
Each diphenyl alkene consists structurally of a string of carbons contained between two phenyl
rings (C6H5). We measure spectra for three of these molecules: butadiene, hexatriene, and
octatetraene which contain 4, 6, and 8 carbons, respectively, in their inner strand. Taking 1.39
as the average carbon-carbon bond in the alkenes, the length of the alkenes from longest to
shortest is: octatetraene (11.12 ) > hexatriene (9.73 ) > butadiene (6.95 ). In allusion to the
particle in a box model, these relative distances define the length of a box in which the number
of electrons is equal to the number of electrons in the pi orbitals of the given moleculei.e. 2 for
each double bond present between the phenyl rings. Therefore the 3 alkenes we use represent 3
2

Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy
boxes of varying sizes. This model applies because the electrons are delocalized throughout the
pi bonds as they would be throughout a 1-D box. The hybridization and combination of orbitals
explains the origin of the molecular orbitals for each of the alkenes, which are filled from lowest
to highest energy as is suggested by the Aufbau principle. Thus, when radiation excites the
electrons to higher energy levels they absorb energy, jumping from the highest occupied
molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) and releasing
photons upon relaxation back to their ground state. The E approximation for the particle-in-abox model above can be applied to the alkene molecules to calculate the lowest energy
transition--from HOMO to LUMO--in the alkene molecules. For each of the alkenes, which have
hybridization of sp3, the HOMO and depend on the number of electrons in the box made up by
the pi bonds in the carbon string. Quantum Dots are crystals of semiconductors with diameters
on a nanometer-sized scale (typically about 1-20 nm). Their absorption and photoluminescence
spectra are determined by their size with a correlation similar to that modeled by aparticle-in-abox. An approximate calculation for the lowest energy transition in a quantum dot is given by:
2

= + 82 +

82

1.8 2

4 . Egap is the value of the energy difference between the

0

valence and conduction band for a non-quantum confined semiconductor, which has a value of
1.74 eV for CdSe, as is the nature of the quantum dots used in our experiment. is the
effective mass of an electron (~(.13)me) and the radius of a sphere, giving the energy of an
electron in a certain size of sphere as the second term. The third term adds the energy of the
hole in the sphere (the positive charge left behind by the electron), with effective mass ,
which is ~(0.45) me. In the final term, which gives a Coulomb potential energy, e gives the
charge on an electron (1.602E-19 C), is the dielectric constant of the semiconductor (~9 for
CdSe dots with 5 nm diameters) and 0 gives the permittivity of vacuum . Thus, the equation
offers a relationship between the lowest energy transition in a quantum dot as a function of
radius, which can be used to estimate the sizes of quantum dots.
Essentially, experimental applications of spectroscopy and analysis of experimentally obtained
data alongside theoretical calculations offer an application of the theories of quantum mechanics
and an evaluation of the accuracy of the many approximations which offer insight into the nature
of molecules and particles on a quantum level, allowing us to better understand the mechanics of
light absorption and emission, diffraction and interference, and the energy transitions which
accompany these processes.
Experimental Methods
1) Diffraction Grating Setup
A diffraction grating set-up demonstrated the diffraction of the red beam of an He-Ne laser
through slits in a grating according to the varying wavelengths of the beam. The laser beam
emitted light at a wavelength of 650 nm. The distance (L) between the grating and screen was
3

Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy
measured, as well as the distance (D) between the undiffracted (zeroth order) and diffracted
points of light. (See Figure 1 schematic)
2) Photoluminescence Spectra
For all photoluminescence measurements of the quantum dots and alkenes, the Ocean Optics
Spectrophotometer settings were adjusted to integration time = 140, average = 50, and boxcar =
20. A dark spectrum was recorded by blocking the UV light. Spectra were then recorded for each
of the linear alkenes and their reference sample--butadiene, hexatriene, octatetraene, and
cyclohexane-- as well as for the quantum dot samples A-F and their reference sample, toluene,
under UV illumination. The wavelength of the peak corresponding to the lowest energy
transition for each spectrum was recorded. Each spectra was saved onto a USB drive for later
analysis.
3)Absorption Spectra
For all absorption measurements of both quantum dots and alkenes, the settings were adjusted to
integration time = 80, average = 20, boxcar = 5. A dark spectrum was recorded. For the alkenes,
a reference spectrum of cyclohexane was recorded before taking spectra of each diphenyl alkene
sample: butadiene, hexatriene, and octatetraene. For the quantum dots, a reference spectrum of
toluene was recorded before taking spectra of each quantum dot sample: A-F. The wavelength of
the peak corresponding to the lowest energy transition for each spectrum (both alkenes and
quantum dots) was recorded and each spectra saved onto a USB drive for later analysis.
Data/Results
Diffraction Grating Measurements
L
D

d
Grating constant (1/d)

76.5 cm
29 cm
22.28o
0.00172 mm
583 lines/mm

Table 1: Shows measurements of diffraction grating set-up.

The grating constant was solved using the diffraction equation:
= =

, giving the number slits/mm.(See figure 1 for schematic).

Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy
Diphenyl Alkene Absorption Energies
Diphenyl Alkene

Lowest
Energy Peak

Estimated length Energy level

of total carbon
transition
string
(ni nf)

Butadiene
Hexatriene
Octatetraene

3.924 eV
3.340 eV
3.137 eV

6.95
9.73
11.12

23
34
45

Expected E
from HOMO to
LUMO
3.90 eV
2.78 eV
2.74 eV

Table 2: The lowest energy peaks correspond to the first absorption peak (lowest energy peak) for each diphenyl
alkene in Figure 2, below. This is the measured energy of the transition from HOMO to LUMO. The theoretical
calculation, given by , =

2
82

(2 2 ) is also shown, using the bond length approximated by the average

1.39 for each carbon-carbon bond and the energy transition (change in n) from the HOMO to the LUMO.

Alkene Absorption
1.8
1.6
Absorbance

1.4
1.2

Butadiene

Hexatriene

0.8

Octatetraene

0.6
0.4
0.2
0
3

Energy (eV)
Figure 2: Plots the absorption spectra of the diphenyl alkenes. The peak of lowest energy gives
the energy of the transition from the HOMO to the LUMO, as seen in Table 2.

Alkene absorption spectra: E between successive peaks

Alkene
Butadiene
Hexatriene
Octatetraene

Peak 1
3.924 eV
3.340 eV
3.137 eV

Peak 2
4.490 eV
3.517 eV
3.324 eV

Peak 3
5.064 eV
3.687 eV
3.492 eV

1st E
0.566 eV
0.177 eV
0.187 eV

2nd E
0.574 eV
0.170 eV
0.168 eV

Avg E
0.570 eV
0.174 eV
0.178 eV

Table 3: The energies of the first three peaks of each alkene in Figure 2 are given, along with the differences in
energy between them.

Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy
Quantum Dot Absorption
Energy Peaks

Quantum Dot Absorption

0.6

Absorbance

A
0.4

B
C

0.2

D
E

0
1.9

2.1

2.3

-0.2

2.5

2.7

2.9

3.1

Quantum
Dot
Sample

Lowest
Energy
Peak
(eV)

A
B
C
D
E
F

2.694
2.445
2.325
2.196
2.083
2.005

Table 4:The lowest energy peak

values shown are the lowest
energy transitions seen in the
absorption spectra of each of
the quantum dot samples, which
can be seen graphically in
Figure 3.

Energy (eV)

Figure 3:Plots the absorption spectra of the nanocrystal quantum dot particle samples.
The peaks of lowest energy correspond to the lowest energy transition for electrons in
each quantum dot sample, which are given as values in Table 4.Sample E absorption
data was obtained from Jeffreys lab group from Section AC.

Quantum Dot
Photoluminescence Peaks

Quantum Dot Photoluminescence

20
A

Intensity

15

Quantum
Dot
Sample

Energy
Peak
(eV)

Toluene
A
B
C
D
E
F

3.365
2.870
2.353
2.240
2.129
2.051
1.945

10

E
1.8

2.2

2.4

2.6

2.8

Energy (eV)
Figure 4:Plots the photoluminescence spectra of the nanocrystal quantum dot particle
samples. The energies shown correspond to the wavelengths of the photons which are
released when electrons relax from excited states back down to the ground state. The peak
for sample B was divided by a factor of 4 to condense the scale of the y-axis.

Table 5:Given are the values

at the photoluminescence
energy peaks of each of the
quantum dot samples, which
can be seen graphically in
Figure 4. Additionally, the
value of the peak of the
reference sample, toluene, is
given, although it is not
included in the accompanying
graph.

Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy

Quantum Dot Energy Calibration

Curve

Quantum Dot
Radius Sizes

Quantum Radius
Dot
Size
Sample
(nm)

Radius (nm)

5
A

A
B
C
D
E
F

0
1.9

2.1

2.3

2.5

2.7

2.9

Energy (eV)
Figure 5: The equation: = +

2
82

82

1.8 2
40

was used to construct a

calibration curve from which the radii of the quantum dot samples could be approximated.
The black line shown is the calibration curve, while the points on the curve show the
estimated radii of each of the quantum dot samples determined from the values (in eV) at
their absorption energy peaks.

1.83
2.10
2.29
2.56
2.90
3.25

Table 6:The calibration

curve was used to
calculate approximate
radii in nm for each of
the quantum dot
samples.

Full Width at Half Maximum for Smallest Quantum Dot

Quantum Dot

Half Max Height

(Intensity)

Low and High

Energy at Half
Max. (eV)

Full Width
Corresponding
at Half Max. range of radii
(nm)

3.31

2.743 & 3.125

0.382 eV

1.54 to 1.79

Table 7: The Full Width at Half Maximum (FWHM) data for the smallest quantum dot particle sample, A, is shown
in the table, which includes the high and low energy points which correspond to half of the maximum value, and a
calculation of their difference giving the breadth of the photoluminescence peak at this point. The breadth
essentially gives a variation in the sizes of quantum dots in the sample, which can be obtained by comparison of the
energy range to the calibration curve.

Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy
Alkene
Photoluminescence Peaks

Alkene Photoluminescence
160
140

Diphenyl
Alkene

Energy
Peak
(eV)

Cyclohexane
Butadiene
Hexatriene
Octatetraene

3.365
3.358
2.562
2.402

120

Intensity

100
80

Butadiene

60

Hexatriene

40

Octatetraene

20
0
-20 1.8

2.3

2.8
3.3
Energy (eV)

3.8

Figure 6: The photoluminscence spectra of the diphenyl alkenes, which corresponds to

the release of photons as electrons fall back to lower energy levels, are shown in the
above graph.The butadiene sample data was divided by a factor of 6 to provide a more
condensed y-axis scale.

Table 8: The energy values at

the photoluminescence peaks
for each of the diphenyl
alkenes are given above, in
addition to the peak for the
reference, cyclohexane, which
is not included in the
graphical representation in
Figure 6.

Stokes Shift: comparison of peaks between spectra

Sample
Species
Butadiene
Alkenes Hexatriene
Octatetraene
A
B
Quantum C
Dots
D
E
F

Absorbance
Peak (eV)
3.924
3.340
3.137
2.694
2.445
2.325
2.196
2.083
2.005

Photoluminescence
Peak (eV)
3.358
2.562
2.402
2.870
2.353
2.240
2.129
2.051
1.945

Difference in
peaks (eV)
-0.566
-0.778
-0.735
+0.176
-0.092
-0.085
-0.067
-0.032
-0.06

Table 9: Data presented in previous tables is reorganized into one in order to allow comparison of the differences
between the peaks of the absorbance and photoluminescence spectra for the alkenes and for the quantum dot
samples. A negative difference indicates that the peak for a particular speceies is at lower energy in the
photoluminescence spectrum than in the absorption spectrum (i.e. it was moved left towards lower energy).

Discussion
Diffraction
Spectroscopy, and therefore photoluminescence and absorption, rest on the principles of
diffraction. Spectrometers contain a diffraction grating which manipulates the path of incoming
8

Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy
light waves depending on their wavelength. These photons can then be counted to give their
intensity and a corresponding spectrum of wavelengths. The diffraction grating set-up
demonstrates the mechanics of diffraction which we employed later to measure
photoluminescence and absorption spectra with a computer processing program and equipment.
Measurements of the distances shown in Figure 1 and a known wavelength of light emitted by
the He-Ne laser allow a calculation of the distance between slits in the diffraction grating, and a
successive calculation of the grating constant, which we found to be about 583 lines per mm.
This number indicates that the pattern of constructive and destructive interference caused by the
interaction of wavelegths which we see on the screenconstructive interference indicated by
visible points of lightis the result of diffracting waves through hundreds of miniscule openings
(each smaller than the wavelength themselves) in the diffraction grating. As the n term
suggests, the light must travel an integral amount of wavelengths in order to result in the
evidence of constructive interference which we see. This constructive interference is the result of
wavefunctions interfering when in phase with each other, meaning that magnitudes of the
wavefunctions are increased when added. Destructive interference, however, which explains the
dark areas between points of light on the screen, results from the out-of-phase interference of
waves, the amplitudes of which cancel each other out.
Alkenes
Absorption spectra of substances measure the transmittance of light waves filtered through the
substance; that is, the ratio of intensity which the substance absorbs over the total intensity which
the substance is exposed to. As can be seen by the plot in Figure 2, the diphenyl alkenes in our
experiment all absorbed similar wavelengths of light, as indicated by the overlapping lines of
their spectra. This, along with the similar shape of the spectra, suggests something of the
similarity in structure among the alkenes. Notably, the shape of the butadiene spectrum differs
from the similar, 3-peaked curve shared by the other two alkenes. This suggests some error in the
measurement of the butadiene absorption spectra, perhaps caused by interference from other
light radiation or incorrect dark and reference spectra recordings. However, the general trends
between the 3 alkenes can still be interpreted from the graphs as shown. The peaks of lowest
energy of each alkene, corresponding to the lowest energy transition of an electron in the
molecule from the HOMO to the LUMO, can be clearly identified in Figure 2 as well. The
energy corresponding to these peaks increases from 3.137 eV in octatetraene to 3.924 eV in
butadiene, as given in Table 2. We approximate the length of the alkenes to be the length of the
carbon string between the two phenyl rings, assuming the bonds in this region to provide a
box in which the electrons are delocalized. According to the average carbon-carbon bond
length, butadiene is the shortest of the three alkenes with an approximate length of 6.95 , while
octatetraene is the longest with a length of 11.12 . The correlation seen here between energy
and bond length is in agreement with that given by the particle-in-a-box model. A shorter box or
molecule length corresponds to a higher energy, while a larger area of delocalization corresponds
9

Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy
to a lower energy. The number of double bonds increases by one for each of the alkenes in order
of increasing length, such that butadiene has two bonds, hexatriene has three, and octatetraene
has four. Each bond corresponds to two electrons placed in an energy level. That is,
butadienes HOMO is the n=2 level, with 2 electrons in each n=1 and n=2, while hexatriene has
two electrons in each of the first 3 energy levels. Following the same trend of the Aufbau
principle of filling orbitals from lowest to highest energy, octatetraenes HOMO is n=4. The
theoretical energy transition values predicted by the particle in a box model are compared with
the experimental values from the measured spectra in Table 2, and it can be seen that they vary
slightly from the experimental values. The expected energy for butadiene most closely models
the spectra data, suggesting that butadiene, with less electrons in its area of delocalization, most
closely models a particle-in-a-box of zero potential. As the number of electrons in the orbitals
of the alkene increases, so does the variance between the experimental and theoretical
calculations. This demonstrates that the effects of interactionsCoulomb repulsions--between
electrons become more pronounced when there are more electrons present, even though they
may occupy a larger area of delocalization.
Comparing the various peaks of the absorbance spectra of each individual alkene in Table 3, it
appears that the distance between peaks is somewhat uniform, and rather small in comparison to
the magnitude of the energies indicated by each peak. The peaks correspond to the various
energies (or wavelengths) of photons absorbed by the substance, which excite the electrons to a
higher energy level. However, the relatively small amount of energy corresponding to the
distance between two peaks is not enough to excite electrons. This can be explained by the
vibrational transitions of the molecule which accompany transitions in the energy states of
electrons. According to the Born-Oppenheimer approximation, the nuclei of a molecule and the
distance between them is fixed, while electronswith a much smaller massmove rapidly
around them. However, this approximation does not accurately model our experimental data,
from which we can see the effects of these vibrations in the energy difference between
successive peaks.
Quantum Dots
The absorption and photoluminescence spectra of quantum dot samples give further insight into
the mechanics of energy transitions of electrons in particles and how the size of the volume the
electron is delocalized in, the size of the box with comparison to the particle-in-a-box model,
influences these energies. Table 4 lists the lowest energy peaks corresponding to the graph of
absorbance spectra in Figure 3. The energy corresponding to the peak of each of the quantum dot
samples increases from F to A, indicating a trend in the increase of absorption of light of shorter
wavelength and higher energy in this order. The spectra for A and D both give negative values of
absorbance, which suggests some experimental error from interference with other spectra,
perhaps from the dark of reference taken, but their peaks follow the trend in increasing energy
established by the other samples. Applying the equation of an approximate solution for the
lowest energy absorption peaks of quantum dots, as given in the introduction above, a calibration
10

Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy
curve which plots energy as a function of the radius of a quantum dot was created and is
presented in Figure 5. The energy values at the lowest energy peak for each quantum dot in
Figure 3 was plotted onto the calibration curve to give an approximation of the radius. As
implied by the calibration curve and by Table 6, there is a correlation between the radius size of
the quantum dots and their lowest energy peak. As the energy at which photons are absorbed
increases (from F to A), radius decreases. That is, smaller quantum dots absorb light at higher
energies and shorter wavelengths, while quantum dots with larger radii absorb light of lower
energy with longer wavelengths. The quantum dots samples A-F ranged in radii from 1.83 nm to
3.25 nm, emphazing the infintesimal scale of these quantum particles.
Within an individual sample, rather than absorbing a single wavelength, a range of wavelengths
is absorbed, indicated by the peaks which have breadth covering a range of energies, rather than
sharp individual points of absorbance. This indicates that within a single sample of quantum
dots, the quantum dots themselves range in size over a span of radii.Table 7 gives the Full Width
at Half Maximum value of the main photoluminescence peak of the smallest quantum dot, A.
This peak differs slightly in shape from the other quantum dot peaks in Figure 4, indicating that
the calculated range may be somewhat off. The trend suggests the peak of sample A should be at
a slightly lower energy. However, the concept is still justified by analysis of the FWHM of A
and could be applied similarly to the other quantum dot samples. For sample A, the radii
corresponding to the range in energy at half of the maximum height of the peak, reprensent the
majority of the range of radii in sample A. Using the calibration curve, we approximate this
range of radii to cover 1.54 nm to 1.79 nm, demonstrating a span of quantum dot radii that
absorb photons of similar wavelength and energy.
Stokes Shift
As absorbance shows the wavelengths of photons which are absorbed by a particular molecule or
substance when electrons are excited to higher energy levels, while photoluminescence shows
the wavelengths of photons which are emitted when electrons relax back down to their ground
state, it follows that the absorbance and photoluminescence spectra of a substance should be very
similar. These trends can be observed in the relationships between the alkenes spectra in Figures
2 and 6, and between the quantum dot spectra represented in Figures 3 and 4. The ordering of the
alkenes and quantum dots in terms of the increasing energies of their peaks is constant across the
absorbance and photoluminescence spectra. The peaks of the alkenes increase in energy such
that: octatetraene<hexatriene<butadiene, while the energies of the peaks of the quantum dots
increase from F to A. It might be expected that the amount of energy released when an electron
relaxes back to ground state would be the same as the amount of energy which was intially
absorbed, which would give peaks that exactly match up across the measured photoluminescence
and absorption spectra. However, the difference between the peaks, as shown in Table 9,
suggests that there is a consistent trend of less energy being released than absorbed. The negative
values throughout the final column of the table indicate that the peaks for the photoluminescence
11

Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy
spectra of a particular sample are generally at lower energy than the corresponding peaks in the
absorption spectra. The exception is A, which has been seen in the graphs to vary from trends,
indicating some experimental data. The general trend here can be explained by the Stokes Shift.
When photons are absorbed and an electron is excited to a higher energy state, some of the
absorbed energy is lost in microscopic vibrations and the production of heat, resulting in an
emission of a lower energy photon. Therefore, the peaks of the photoluminescence spectra are at
lower energies due to the energy lost by the electron between absorption and emission.
Conclusion
Spectroscopy is a technique of great importance in chemistry and for the general scientific
communtiy, employing the mechanics of wave diffraction to allow observation and data analysis
of electronic transitions between energy states through the processes of absorption and emission.
Diffraction relies on the properties of waves in order to diffract radiation of varying wavelengths
in different directions. Resultingly, for use in spectrometry, the intensity of a particular
wavelength can be measured.
This spectroscopy experiment allowed a comparison of theoretical calculations, such as those
presented by the particle-in-a-box model, with experimental data. Three diphenyl alkenes and
several samples of quantum dots were analyzed by absorbance and photoluminescence spectra.
The alkenes paralleled a particle-in-a-box model in that electrons delocalized throughout the pi
bonds in their central carbon string acted similarly to a particle in a box. They were excited from
the HOMO to the LUMO by incoming photons of light. A correlation between the length of the
alkene carbon string and the energy peak of the spectra was seen in that a shorter length
corresponded to higher energy transitions. The quantum dots represented a range of sizes, radii,
which could be approximated by a calibration curve relating the radius of the quantum dot to the
energy which it absorbed. The radii for each of the quantum dot samples was approximated and
found to be on a scale of only a few nm. Within each sample, the radii of the quantum dots
varied by a small range. The wavelength of light that each quantum dot absorbed or emitted was
dependent on the size of its radii, with larger quantum dots absorbing and emitting photons of
longer wavelength, and smaller quantum dots absorbing and emitting photons of shorter
wavelength and higher energy. The Stokes Shift concept explains the relationship between
photoluminescence and absorption spectra. Electrons that are excited to higher energy levels lose
some energy to vibration, resulting in a lower energy of the photons emitted. Thus, the peaks of
the photoluminscence spectra were generally found to be at lower energies than those of the
absorption spectra.

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Chem 155 AC

Lab Five Report

Mackenzie Kyle Kilmer

March 12th, 2013

Electronic Spectroscopy

Calculations
1.) Diffraction Grating Constant: = =

Note: n = 1 (because weve measured the distance between two points of constructive
interference).
1

= 650 nm 106 = 6.5E-4 mm = n

29

= 76.5 = 0.379

= =

6.54
0.379

2.) Conversion from to eV: = =

=

(6.63E34 J s)(3.0E8 m)
178.07

grating constant = = 0.00172 =

= 0.00172 mm

109
1

= 6.63E-34 J s

583

= 3.0E8 m/s

1.60219 = 6.972 eV

3.) Theoretical E of lowest energy transition of alkenes (HOMO to LUMO):

2
, =
(2 2 )
82
For butadiene: n = 2 n = 3 L = 6.95 = 6.95E-10
(6.63E34 J s)2

E = (8)(9.10931 )(6.9510)2 1.60219 (9 4) = 3.90 eV

4.) Energy for Quantum Dot Radius Calibration Curve:

= + 82 +

82

1.8 2

Egap = 1.74 for CdSe Quantum Dots

h = 6.63E 34 J s
m*e = 0.13(9.1093819E-31 kg)
m*h = 0.45(9.1093819E-31 kg)
e = 1.602E-19 C
= ~9 for our quantum dots
o = 8.854E-12 C2 /J m
A calibration curve was made in Excel by plotting E as a function of a (in nm) for various values
of a.

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