Fockler 1

MaKenzie Fockler

Soumya

10 March 2016

Lab 5: Electronic Spectroscopy of Polyenes and Nanoparticles

Introduction:

In the experiment, absorption and photoluminescence spectra of linear alkenes and

nanoparticle quantum dots were collected using a spectrometer to record wavelength of absorbed

or emitted photons within the electromagnetic spectrum of infrared to ultraviolet light. Normally

in an atomic orbital, this wavelength corresponds to a lowest energy transition from a ground

state of electron configuration to that of an excited state by using the particle in a box

𝑛2 ℎ 2
explanation of the Schrodinger equation: 𝐸𝑛 = 8𝑚𝐿2. Where n is the energy level, h is Planck’s

constant, m is the mass of the electron, and L is the length of the box. This illustrates how energy

is proportional to the relative length of the box.

However, linear alkenes are molecules which are composed of carbon atoms localized in

sp^2 structures, leaving two unpaired antibonding electrons per double bond, thereby forming an

antibonding pi orbital based on the reduced electron density of the carbon atoms. The energy

difference in the alkenes for the first peak of the graphs, the transition between HOMO (highest

occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital), can be calculated

(2𝑛+1)ℎ2
by the equation: 𝐸𝑛+1,𝑛 = , where n is the HOMO and the other constants are the same
8𝑚𝐿2

as above. The length, L, of the alkene can be calculated by multiplying the number of carbon-

carbon bonds by the average length of a carbon bond, 1.39 angstrom. By examining the

molecular orbitals, HOMO is determined to be 2 for butadiene, 3 for hexatriene, and 4 for

octatetraene. The quantum dot also used the particle in a box explanation but in a complex 3D
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format. An approximate solution in order to solve for the quantum dot radius of each sample can

be calculated from the equation: ., where Egap is the band

gap, or the energy difference between the conductive band and the valence band, which is 1.74

eV for CdSe, me* is the effective mass of an electron, a is the radius of the sphere, and the last

term is the confinement energy of the hole in the sphere with radius a and the coulomb potential

energy. This equation is only valid for the lowest energy exciton, which is a bound electron/hole

pair.

Finally, in the lab, the diffraction of a helium neon laser was analyzed. Through this, we

were able to measure the grating constant, N, by the equation: N = 1/d; where d = the distance

between grates. “d” is calculated from the equation d sin(theta)= n(wavelength). The diffraction

constant is measured in lines/mm.

Procedure:

First, the grating constant was determined by measuring the distance between the He-Ne

laser and the wall. This value was recorded as distance L. Then the distance between the

undiffracted line of light and the other closest visible dot was measured and recorded as distance

D.

Then, the absorption of the alkenes were determined using the Ocean Optics UV/VIS

Spectrometer. The spectrometer had to be set to absorbance mode and cyclohexane was used as a

reference. The machine was calibrated by setting the dark spectrum to match that of the

background radiation. The absorbance spectra of butadiene, hexatriene, and octatetraene were

measured and saved to a USB for a range of 350nm to 700nm. Additionally, the absorption of

the quantum dots was measured and recorded by repeating the process, except using toluene as

the reference instead of cyclohexane.

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The photoluminescence spectra of the cyclohexane reference and the alkenes under UV

illumination was measured and saved. For the photoluminescence measurements, the

spectrometer was set to an integration time- 100msec, averages=50, and boxcar=20. The process

was repeated with the CdSe nanoparticles, using toluene as the reference instead of cyclohexane.

The photoluminescence data for all quantum dots were measured and saved.

Results:

L= 1 meter; D= 38 cm

d=.001665; N=600.5 lines/mm

Absorbance of Polyalkenes at different energies

2

1.5

1
Absorbance

0.5
Butadiene
0
0 1 2 3 4 5 6 7 8 Hexatriene
-0.5
Octatetraene
-1

-1.5

-2
Energy (eV)

Graph 1: Spectra of absorbance of butadiene, hexatriene, and octatetraene at various energies.

The first peaks were used to determine experimental electron transition values between HOMO

and LUMO, and then were compared to theoretical values.

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Electron transition energies:

n L Theoretical Experimental ΔEn+1,n Percent Error

ΔEn+1,n (lowest energy peak)
Butadiene 2 6.95 3.893 3.915 0.56

Hexatriene 3 9.73 2.781 3.358 20.7

Octatetraene 4 12.51 2.163 3.148 45.5

Table 1: The data shows the theoretical and experimental energies difference between the n

(HOMO) and n+1 (LUMO) energy levels. The percent error acts as a comparison between the

theoretical and experimental energies. L and n are used to calculate the theoretical energy.

Absorbance peaks of Alkenes

Lowest eV Peak 2nd Lowest Third Lowest eV Peak Peak Difference

eV Peak (N+1) – N

Butadiene 3.873 4.507 5.516 0.634

Hexatriene 3.324 3.537 3.737 0.213

Octatetraene 3.148 3.351 3.535 0.203

Table 2: The table shows the energy levels at which the peak absorbance of the alkenes occurred,

and the energy difference between the lowest and second lowest energy peaks.
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Peak Intensity of Photoelectrons from Different Alkenes that

Correspond to Specific Energies
3500

3000

2500

2000
Intensity

Butadiene
1500
Hexatriene
1000
Octatetraene
500

0
0 2 4 6 8
-500
Energy (eV)

Graph 2: Photoluminescence spectra for the alkenes (butadiene, hexatriene, octatetraene). The

peaks were used to determine the energy difference between HOMO and LUMO and thus, the

type of photon emitted.

3rd Highest 2nd Highest Highest Energy Energy Difference Type of

Energy Peak Energy Peak Peak (eV) (N+1) - (N) (eV) photon
(N) (eV) (N+1) (eV)
Butadiene 3.171 3.318 3.463 .147 infrared
Hexatriene 2.586 2.776 2.923 .190 infrared
Octatetraene 2.259 2.455 2.569 .196 infrared
Table 3: The peaks of the photoluminescence of the alkenes, with the energy difference being the

energy of the photon emitted as the electron goes from LUMO (n+1) to HOMO (n) in electron

volts. All photons emitted fall within the infrared range.

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Graph 3: The graph depicts the spectra of the absorbance of the different nanoparticles at varying

wavelengths, translated into different energies in eV. It is used to determine peak energies for

Table 4.

Graph 4: The graph depicts the spectra of the photoluminescence of the different nanoparticles at

varying wavelengths, translated into different energies in eV. It is used to determine peak

energies for Table 4.

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Lowest Highest Energy Quantum Dot Quantum Dot

Energy Peaks Radius from Radius from
Peaks Photoluminescence Lowest Energy Highest Energy
Absorbance (eV) Peaks of Peaks of
(eV) Absorbance (m) Photoluminescence
Red 3.453 3.372 1.39 1.30
Orange Red 3.467 2.031 1.39 3.12
Orange 3.522 2.103 1.37 2.83
Yellow 3.474 2.216 1.39 2.52
Green Yellow 3.499 2.301 1.37 2.33
Green 3.446 2.396 1.40 2.18
Table 4: The table shows the lowest energy peak from the absorbance spectra and the highest

energy peak from the photoluminescence spectra for the quantum dots. The peaks were then

translated into the radii of the quantum dots by using the 3D particle in a box approximation

equation given in the introduction. Note that the red quantum dot does not follow the trend in the

radii size that the other quantum dots follow with changing color.

Energy
Energy of nanoparticles of varying radii
12 Red

10 Orange Red

8
Energy (eV)

Orange

6
Yellow
4
Green
2 Yellow
Green
0
0 2E-09 4E-09 6E-09 8E-09 1E-08 1.2E-08 1.4E-08
Radius (meters)

Graph 5: The graph shows the effect of radius size on the energy of the quantum dot in eV. This

graph is beneficial in seeing the logarithmic trend of the formula of the 3D particle in a box

approximation formula. However, all of my data points are extremely close together in their
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radii, which makes it difficult to tell the significance or trend of the experimental data. The graph

uses the set of radii that were calculated based off the lowest energy absorbance peaks.

Energy of nanoparticles of varying radii Energy

3.8
Red
3.7
Orange Red
3.6
Energy (eV)

Orange
3.5

3.4 Yellow

3.3 Green
Yellow
3.2
Green
1.3E-09 1.32E-09 1.34E-09 1.36E-09 1.38E-09 1.4E-09 1.42E-09 1.44E-09 1.46E-09 1.48E-09
Radius (meters)

Graph 6: Therefore, this graph is a magnified version of graph 5, in an attempt to make the

experimental data show more clearly, and show that as radius increases, the energy transition of

the quantum dot decreases.

Determination of FWHM:

Smallest quantum dot: Green

Height= 1552.13-1268.55=283.76 intensities

Half maximum= 1552.13-(.5*286.76)= 1410.25 intensity

Approximate half maximum energies: 2.279 eV, 2.449 eV

2.449-2.279= .170 eV

FWHMx2= R@2.449-R@2.279= (2.1x10^-9)-(2.38x10^-9)= -2.8x10^-10

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Highest energy peak Second Highest Energy Third Highest Energy Average

Peak Peak Difference

A PL Diff A PL Diff A PL Diff

Butadiene 5.516 3.463 2.053 4.507 3.318 1.189 3.873 3.171 0.702 1.31

Hexatriene 3.737 2.923 0.814 3.537 2.776 0.761 3.324 2.586 0.738 0.77

Octatetraene 3.535 2.569 0.966 3.351 2.455 0.896 3.148 2.259 0.889 0.92

Table 5: The table shows the difference between the photoluminescence peaks (PL) and

absorbance peaks (A) of the alkenes, which are used to quantify Stoke’s shift.

Absorbance Peak (eV) Photoluminescence Peak Difference

(eV)
Red 3.453 3.372 0.081
Orange Red 3.467 2.031 1.436
Orange 3.522 2.103 1.419
Yellow 3.474 2.216 1.258
Green Yellow 3.499 2.301 1.198
Green 3.446 2.396 1.05
Table 5: The table shows the difference between the photoluminescence peaks (PL) and

absorbance peaks (A) of the quantum dots, which are used to quantify Stoke’s shift.

Discussion:

In the first part of the lab, we measured the distance between the diffraction grating and

the wall to be 100 cm with the points of laser light being separated at a distance of 38 cm.

Therefore, the diffraction grating constant was calculated at 600.5 lines/mm in a first order

setting. Light can be perceived as a wave front that is diffracting as light is reflected off of two

slits; the constructive interference of these two wave fronts highlights a light spot on the table

separated by the dark spots of deconstructive interference.

When calculating the electron transition energies, the experimental values became

increasingly different from the calculated theoretical values as the alkene molecule grew longer.
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As the length of the molecule increases, the approximation of the energy transition from particle

in the box becomes less accurate due to the increasing number of electrons and pi orbitals.

When analyzing the absorbance data for the alkenes, each alkene had three peaks close

together, which are a result of the different energy levels, with the first peak being the ground

state, The three peaks are also seen in the alkene photoluminescence spectra, in which the

distance between the peaks is the amount of energy released as a photon as the electron decreases

excited states. The energy difference between the peaks indicated that the photon released should

be infrared, which was the expected outcome.

The peaks from the absorbance and photoluminescence spectra of the quantum dots were

used to determine the radii of the quantum dots by using the 3D particle in a box approximation

stated in the introduction. However, the resulting radii have some error in their values, because

green and red were calculated to have the two lowest radii, but are far away from each other on a

color spectrum. It is likely that the red quantum dot data had some significant error in its

collection, because with the exception of red, the quantum dots had a decreasing radius as the

quantum dots changed from orange-red to green. Red should have had the largest radius.

Additionally, the radii that were calculated for the quantum dots were much closer together than

expected, so there was some other systematic error in the data that must have affected the

absorbance values of the quantum dots. The lab set up seemed to be problematic and it is not

surprising that some of the data is inaccurate because the absorbance spectrometers were having

many issues during lab.

Next in the lab, the green quantum dot was used to determine the full width at half

maximum. Although my data actually indicated that red was the smallest quantum dot, I did the

calculations for the green quantum dot instead, because I suspect there is significant error for the
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red one. The FWHM was determined to be .170 eV, or 2.8x10^-10 as the quantum dot size

distribution. The main difficulty in applying the Gaussian curve and FWHM to the experimental

data is that all of the calculated radii are too close together to determine a significant dependence

of energy on size of the quantum dot.

Finally, the relevant energy peaks of the absorbance and photoluminescence spectra were

compared and it is seen that the shift of the energies (Stoke’s Shift) was due to a relaxation in the

vibrational levels of the excited state of the molecule from the transition of pi to pi * and back

down from pi* to pi. This loss of potential energy especially in the linear alkenes can be

explained due to the fundamental speeds of the nucleus and electron according to the Franck-

Condon principle where the faster moving electron density has a higher probability of

transitioning together as a unit if the vibrational wave functions of each vibrational state promote

constructive interference in phase within the same instance of a reaction coordinate. This was

one of reasons why the absorbance and photoluminescence peaks should have looked like mirror

images; the magnitude of energy transitions of absorbance should have matched that of the

emission spectrum even when the starting energies of photoluminescence were much lower.

Conclusion:

In conclusion, the energy transition of an electron from the ground state to the first

excited state decreases in alkenes as the length of the alkene decreases, but the accuracy of the

particle in a box model also decreases as the length increases. The photons emitted by electrons

in alkenes moving from LUMO to HOMO are infrared. From the photoluminescence spectra of

the quantum dots, it can be concluded that the radius of the nanoparticles decreases as the color

progresses from orange-red to green due to green having higher energy peaks. Unfortunately, the

absorbance spectra were very inconclusive due to all of the peaks being similar, and thus having
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similar radii. Because of the lack of significant difference in the radii of the quantum dots, it was

difficult to create a Gaussian distribution of the size or energy of the quantum dots. Finally, the

difference between the photoluminescence peaks and the absorbance peaks can be explained by

the stoke shift and the Franck-Condon principle.