Laboratory Experiment

pubs.acs.org/jchemeduc

Particle in a Disk: A Spectroscopic and Computational Laboratory

Exercise Studying the Polycyclic Aromatic Hydrocarbon Corannulene
E. Ramsey Frey, Andrzej Sygula, and Nathan I. Hammer*,

Department of Chemistry and Biochemistry, University of Mississippi, University, Mississippi 38677, United States

Department of Chemistry, Mississippi State University, Mississippi State, Mississippi 39762, United States
*
S Supporting Information

ABSTRACT: This laboratory exercise introduces undergraduate chemistry

majors to the spectroscopic and theoretical study of the polycyclic aromatic
hydrocarbon (PAH), corannulene. Students explore the spectroscopic properties
of corannulene using UVvis and Raman vibrational spectroscopies. They
compare their experimental results to simulated vibrational spectra and the
molecular structure obtained from computational chemistry to other PAHs,
including C60. The delocalized electron in corannulene is also conceptually
explored using the particle in a disk model. This laboratory exercise allows
students to explore multiple physical chemistry concepts in one, 3 h laboratory
exercise centered around one theme.

KEYWORDS: Upper-Division Undergraduate, Physical Chemistry, Hands-On Learning/Manipulatives, UVvis Spectroscopy,

Raman Spectroscopy, Computational Chemistry, Nanotechnology, Laboratory Instruction

INTRODUCTION
The physical chemistry laboratory course in many chemistry
departments has been scaled back from the traditional two-
semester period to just one with the number of hours also
reduced to a single credit hour.1 This reduction has a variety of
origins, including the reduction of the number of hours in
liberal arts majors and the introduction of new specialty courses
such as environmental and forensic chemistry. A challenge,
therefore, is the ability to provide students with enough
laboratory experience that covers all of the important areas of
physical chemistry including thermodynamics, kinetics, spec-
troscopy, and quantum chemistry in a one credit hour course in Figure 1. Molecular models of the popular polycyclic aromatic
a single semester. Here, we show that the study of the hydrocarbon nanomolecular building blocks. A, Pyrene; B, perylene;
C, corannulene (head-on); D, corannulene (rotated to show
nanomaterial building block corannulene (see Figure 1) oers
curvature); and E, buckminsterfullerene (C60).
instructors the opportunity to cover a variety of concepts in a
single physical chemistry laboratory meeting. These include the
study of nanomaterials, quantum chemistry, vibrational spec-
troscopy, UVvis absorption spectroscopy, and a conned organic synthesis,3 and now multiple pathways exist for the
particle problemthe particle in a disk.2 By studying synthesis of corannulene, even on the kilogram scale.8 With a
corannulenes physical properties both experimentally and molecular formula of C20H10, corannulene is composed of one
theoretically, students are introduced to not only the use of cyclopentane ring fused with ve benzene rings and can be
spectroscopic techniques such as UVvis and Raman spectros- thought of as one-third of the important molecule buckmin-
copies in the study of nanomaterials but also computational sterfullerene, C60.9 The aromaticity that corannulene and other
chemistry and modeling in the laboratory setting. PAHs possess is an advantageous chemical property in which a
Corannulene is a polycyclic aromatic hydrocarbon (PAH), conjugated ring of unsaturated bonds and empty orbitals
meaning it is composed of fused aromatic rings that contain exhibits a stabilization stronger than that which would be
only carbon and hydrogen. It belongs to the novel subclass of expected by the stabilization of conjugation alone.10
the curved-surface PAHs known as buckybowls or fullerene
fragments.37 It was rst isolated in 1966 by a multistep
XXXX American Chemical Society and
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Journal of Chemical Education
PAHs such as corannulene, as well as fullerenes, generally
absorb light in the ultraviolet and visible regions of the
electromagnetic spectrum and also strongly uoresce because
of the -electron conjugated systems. This makes them very
useful molecular electronic building blocks11,12 for light
harvesting1315 and photoemission applications.1618 PAHs in
general, and corannulene in particular, are thus good models to
illustrate the photophysical properties of electronically active
nanomaterials for students.19,20 The absorption and emission
ranges of PAHs vary due to a number of factors including the
substituent group, conjugation length and branching, and
molecular symmetry. Because corannulene is an organic
molecule, it also dissolves well in organic solvents such as
toluene, cyclohexane, methylcyclohexane, isopentane, and
dichloromethane.21
The availability of corannulene on a large scale allowed for
the synthesis of its several derivatives57an important feature
for applications that use nanomolecular building blocks with
designer properties. Because of the growth in research in the
eld of nanotechnology and the desire to engineer materials
with tunable photophysical properties, the study of molecular
building blocks such as corannulene and other PAHs continues
to rapidly accelerate. For example, complementarity of the
concave surfaces of corannulene and other buckybowls with the
convex surfaces of fullerenes brings about a possibility to
construct molecular clips and tweezers with the potential for
the formation of supramolecular assemblies with fullerenes.22
Although corannulene has only been available commercially
for a short time, a number of experimental and theoretical
studies have explored its photophysical properties. In 2006,
Yamaji et al. reported on absorption and uorescence spectra of
corannulene in cyclohexane at 295 K.21 Absorption peaks were
observed around 260 and 290 nm in an absorption range of
about 220300 nm. The uorescence spectrum for corannu-
lene reveals a broad peak around 450 nm. In 2008, Rouille et al.
reported on the infrared and Raman spectra of corannulene
grains embedded in polyethylene or CsI pellets.23
The illustration of the particle in a box model in the
undergraduate physical chemistry laboratory, using the
absorption spectra of linear-conjugated dye molecules, is a
favorite experiment in many chemistry departments.24,25 In the
classic experiment, the absorption spectra of three cyanine dyes
are recorded, and the lengths of the conjugated orbitals are
determined from the measured absorption maxima. Conned
particle problems that possess distinctive geometries and
boundary conditions oer physical chemistry students unique
challenges, and many variations have appeared in this journal.
Examples include the one-dimensional particle in a box,2426
two-dimensional particle in a box,27 particle in a one-
dimensional champagne bottle,28,29 particle in an isoceles
right triangle,30 particle in an equilateral triangle,31 particle in a
sphere,2,32 and particle in a disk2 models. As in the case of the
cyanine dye experiment, the electronic energy levels of C60 (see
Figure 1) can be described by the particle in a sphere model,2,32
and the allowed transitions can be compared to the
experimental absorption spectra of C60 in hexane.33 The
present laboratory exercise is oered not as a replacement to
the traditional cyanine dyes experiment but rather as an
additional option for instructors who wish to combine multiple
concepts into one laboratory exercise. Newhouse and McGill
previously derived the particle in a disk model in this journal,2
and a brief summary of their derivation is included in the
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Laboratory Experiment
student handout. The energy levels of the electron in the disk
are given by
m2 , n2
Em , n =
2rb2 (1)
where is the mass of the electron, rb is the radius of the disk,
and m,n is the nth root to the mth order Bessel function. The
m,n values are thus the quantum numbers of interest, although
a direct correlation to the molecular orbitals in corannulene is
not possible as is the case in the linear cyanine dyes experiment
and in the case of C60. Students, however, can determine rb for
corannulene using the results from the electronic structure
calculations and measuring the diameter (across terminal
carbon atoms). The diameter of corannulene, optimized using
the B3LYP/6-31+G* level of theory, is 6.5 , which means rb =
3.25 .
EXPERIMENTAL DETAILS
This laboratory exercise was performed for two semesters in a 3
h physical chemistry laboratory class. Corannulene was
obtained from two dierent sources. It was synthesized by
one of the authors (A.S.) and was puried by recrystallization
using ethanol. Corannulene was also purchased from TCI
America (Portland, Oregon), and C60 was purchased from
Aldrich. Perylene bisimide (PBI, a perylene derivative) and
pyrene were synthesized by co-workers at the University of
Mississippi. The UVvis absorption spectra of corannulene,
C60, pyrene, and PBI were obtained in cyclohexane using a Cary
100 Bio UVvis spectrophotometer. The Raman spectrum of
corannulene was recorded using the 514.5 nm laser line from
an Ar+ laser and microRaman spectrometer, as described
earlier.34
Theoretical calculations that used the Gaussian software
package35 were performed prior to data acquisition so that the
students could visualize the geometry and normal modes of
corannulene. The GaussView36 software program was em-
ployed to construct corannulene, although other graphical
drawing packages could be employed. Using GaussView,
students can start with the built-in geometry of C60 and delete
atoms until only C20 remains. Ten hydrogen atoms are then
added to the outer benzene rings to complete the structure.
The symmetry of corannulene should be constrained to the C5v
point group. An optimization and frequency calculation with
Raman intensities was performed using either the HF method
or the B3LYP density functional method and the 6-31+G* basis
set, depending on the speed of the computers to be used for the
laboratory exercise. Instructors may wish to have their students
compare their results using other methods such as semi-
empirical or the MP2 method and also examine the eects of
changing the size of the basis set. After the calculations are
completed, students construct simulated Raman spectra from
the vibrational frequencies and Raman intensities by summing
the Lorentzian functions of each normal mode.1 Alternately, if a
Raman spectrometer is not available, students could obtain an
infrared absorption spectrum in a salt pellet or by using an
attenuated total reection Fourier transform infrared spec-
trometer (ATR-FTIR) and then compare their experimental
results to the simulated infrared spectra. The derivation of the
particle in a disk model can be introduced to the students as an
extension to the particle in a box model in the prelaboratory
lecture. A variation of this laboratory exercise involves the
modeling of the vibrational frequencies of C60 and the
Journal of Chemical Education
calculation of the excited states of both corannulene and C60
using the ZINDO semiempirical method or the B3LYP time-
dependent density functional theory (TDDFT) method as
demonstrated by Rouille et al.23 Although the results of the
ZINDO method will be much quicker, the TDDFT results
match better with the experiment. These additional computa-
tional chemistry exercises (including calculations that use larger
basis sets and the MP2 method) will likely require more time
than allotted for one class meeting and may require students to
start their calculations and then return for the results at a later
time. Further details are provided in the Supporting
Information.
RESULTS AND DISCUSSION
Seven students performed this laboratory exercise at the
University of Mississippi in 2012, and eight students performed
it in 2014. After a brief 15 min prelaboratory discussion about
the particle in a disk model and nanomaterial building blocks in
general, students in pairs constructed corannulane using
GaussView software starting from C60 as a basis and then
started the combined optimization and frequency calculations
using Gaussian 09. As a group, the students then acquired the
UVvis spectra of the four PAHs and studied the dierences
between them. The students then acquired the Raman
spectrum of corannulene as a group. After data acquisition,
the students explored the location in wavenumbers of normal
modes using GaussView and compared the simulated spectrum
in GaussView to the experimental spectrum they had just
acquired. The students also animated the normal modes in
GaussView in order to visualize which ones yielded the
strongest experimental intensities.
Figure 2 shows the UVvis absorption spectra of
corannulene compared to those of C60, pyrene, and PBI. PBI
Figure 2. Comparison of the UVvis absorption spectra of the PAHs
corannulene (C20H10), buckminsterfullerene (C60), perylenebisimide
(PBI), and pyrene.
exhibits the lowest energy absorption spectrum, while pyrene,
C60, and corannulene have features at much higher energies.
Corannulenes high symmetry (C5v) results in a number of
forbidden electronic transitions and thus uoresces in the blue.
Despite its high symmetry, C60 displays many available
electronic transitions in the visible region of the spectrum
and exhibits absorption peaks from 200700 nm.33 The most
dominant transitions, however, lie below 400 nm.
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Laboratory Experiment
Figure 3 compares the experimental and theoretical Raman
spectra from 1501650 cm1 for solid state corannulene. The
Figure 3. A, Comparison of theoretical and experimental Raman
spectrum of corannulene; B, normal mode displacements of the most
intense Raman active mode at 1430 cm1.
agreement between the experiment and theory is very good and
illustrates to students the usefulness of modeling the properties
of new materials theoretically. This is especially true in the
design of new materials where the properties can be simulated
prior to synthesis. Students can visualize the atom displace-
ments of the dierent normal modes using a program such as
GaussView,36 Molekel,37 Molden,38 Jmol,39 or Vibalizer.40
Shown in Figure 3, panel B is a representation of the motion
of the atoms in the most intense normal mode at 1430 cm1
(ring breathing mode). In this mode, the central pentagon
expands and contracts while carboncarbon bonds in the
surrounding hexagons also stretch. The surrounding hydrogen
atoms also bend. After the laboratory period, the students can
construct their own simulated Raman spectra from the
computed vibrational frequencies and Raman intensities by
summing Lorentzian functions for each normal mode.1
The 2014 physical chemistry laboratory class participated in a
survey about the exercise. The survey consisted of ve
questions:
(1) Did you nd the study of nanomolecular building blocks
and in particular, corannulene, interesting and useful?
(2) Did you learn about the use of electronic (UVvisible
absorption) and vibrational spectroscopy and in
particular, Raman spectroscopy, to study nanomaterials?
(3) Did you learn about the use of quantum chemistry to
study the optimized molecular structure, vibrational
energy levels, and motions of dierent normal modes
in corannulene?
(4) Did you nd it useful and enlightening to compare the
experimental vibrational spectroscopy results to the
theoretical simulations?
(5) Did you nd the particle in a disk model interesting?
The participants were asked to respond on a four-point scale
where 0 represented strongly disagree, 1 represented
disagree, 2 represented neutral, 3 represented agree, and
Journal of Chemical Education
4 represented strongly agree. The average responses are
indicated in Table 1. All of the average responses were at least
Table 1. Distribution of Student Responses to Survey
Regarding the Laboratory Exercise
Question Average Responsea (N = 8)
1 3.4
2 3.2
3 3.6
4 3.8
5 3.0
a (5) Sygula, A. Chemistry on a Half-Shell: Synthesis and
Scale used ranged from 0 (strongly disagree) to 4 (strongly
agree).
3.0, which indicates that the students agreed that components
of the laboratory exercise were interesting and useful and that
they also learned about the use of UVvis and vibrational
spectroscopies and quantum chemistry to study nanomaterials.
Interestingly, students agreed most with the statement that the
comparison of the experimental vibrational spectroscopy results
to the theoretical simulations was useful and enlightening.
CONCLUSIONS
This laboratory exercise oers students the opportunity to
study both experimentally and theoretically the properties of
the unique nanomolecular building block corannulene and
compare its properties to other PAHs in one laboratory setting.
Students learn how to employ computational chemistry to
predict the physical properties of such building blocks and are
also introduced to the particle in a disk model. When surveyed,
students indicated that they found the comparison of the
experimental vibrational spectroscopy results to the theoretical
simulations very useful and enlightening.
ASSOCIATED CONTENT
*
S Supporting Information
Instructor notes and a sample student handout. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: nhammer@olemiss.edu.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
N.I.H. would like to acknowledge support from the U.S.
National Science Foundation EPS-0903787 and NSF-0955550
as well as the University of Mississippi College of Liberal Arts,
Department of Chemistry and Biochemistry, Oce of Research
and Sponsored Programs, the Sally McDonnell Barksdale
Honors College, and the NSF-funded Ole Miss Physical
Chemistry Summer Research Program REU (CHE-1156713).
A.S. thanks the Oce of Science, U.S. Department of Energy
for the support through Grant No. DE-FG02-04ER15514. The
authors would also like to acknowledge Kristina Cuellar, Louis
McNamara, Samantha Reilly, John Kelly, and Debra Jo
Scardino Sage for their contributions to the development of
this laboratory exercise and Daniell Mattern and Jared Delcamp
for the synthesis of PBI and pyrene, respectively.
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Laboratory Experiment
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