Information • Textbooks • Media • Resources
Naphthalene and Azulene I: Semimicro Bomb Calorimetry
and Quantum Mechanical Calculations
Carl Salter
Department of Chemistry, Moravian College, Bethlehem, PA 18018
James B. Foresman
Physical Sciences Department, York College of Pennsylvania, York, PA 17405
At its best, any physical chemistry laboratory experiment
should be an investigation of molecular structure and its ef-
fect on physical properties. When experimental data are col-
lected, they should be analyzed with the molecular level in
mind. The most effective way to achieve this is to complement
the experimental work with theoretical calculations. In the
past, when electronic calculations were included in lab ex-
periments, the theoretical methods were usually crude and
approximate. The best example of this is probably the classic
experiment on the UV–visible absorption spectra of a series
of carbocyanine dyes, in which the π electrons are treated
using the particle-in-a-box model (1): the agreement between
theory and experiment is no better than qualitative. With
the advent of more powerful desktop computers and the avail-
ability of computational chemistry software for these plat-
forms, it is now reasonable to expect undergraduate chemistry
students to perform sophisticated quantum mechanical cal-
culations that yield quantitative agreement with traditional
lab experiments. An excellent example has recently appeared
in this Journal, in which the measurement of the rotation–
vibration IR absorption spectrum of HCl is accompanied by
detailed quantum mechanical calculations (2).
One effective way to introduce students to the importance
of quantum mechanical effects is to compare the properties
of two molecules that superficially appear to be similar. In
this series of papers we will describe laboratory exercises that
perform detailed experimental and theoretical comparisons
of two geometric isomers of C10H8: naphthalene and azulene.
The logical place to begin such a comparison is with total
energies: Which isomer is more stable and why? Since the
molecules are isomers, a direct measure of their relative
stability can be made using the difference between their heats
of combustion. This difference, while not large, can be
measured by an apparatus that is common in the undergradu-
ate physical chemistry lab: the bomb calorimeter. Although
simple theories involving aromatic stabilization can correctly
predict which isomer is more stable, calculating an accurate
energy difference demands the use of a high level of theory.
The goal of this experiment is to compare the heats of com-
bustion of azulene and naphthalene and to relate the observed
difference to theoretically computed differences in the energy
of the two molecules.
Background
Naphthalene and azulene are both aromatic hydrocar-
bons and have the same molecular formula, C10H8, but they
differ geometrically.
naphthalene azulene
JChemEd.chem.wisc.edu • Vol. 75 No. 10 October 1998 • Journal of Chemical Education
For both naphthalene and azulene, valence bond structures
can be drawn that contain five C–C single bonds, five C–C
double bonds, and eight C–H bonds. A simple bond energy
calculation would naively predict that the two molecules have
equal heats of combustion.
Both naphthalene and azulene are aromatic. Most students
assume that naphthalene is more stable because more resonance
structures can be draw for it than for azulene (3 vs 2) and
because its bond angles should be closer to 120° for pure
sp2 bonding. The properties of azulene suggest that it has
significant contribution from a structure in which the
seven-membered ring has donated a π electron to the five-
membered ring.
This structure accounts for azulene’s large dipole moment,
its intense charge-transfer absorption in the visible region, and
its tendency to undergo electrophilic aromatic substitution at
the five-membered ring. The electron transfer allows both
rings to be aromatic, but the charge separation requires energy;
so the net effect is that azulene’s π system is more energetic
than naphthalene’s.
Simple theories of resonance predict that azulene, as a
nonalternant hydrocarbon, does not gain as much stability
by resonance as does naphthalene; more sophisticated theories
of aromaticity also support this conclusion (3). For students
the experiment can be explained as an attempt to measure
the difference in resonance energies of the two aromatic mol-
ecules. We know of only one other undergraduate experiment
involving the measurement of resonance energy (4).
Since the two molecules are isomers, they have the same
combustion reaction:
C10H8(s) + 12 O2(g) → 10 CO2(g) + 4 H2O(l)
The difference in heats of combustion immediately reflects
the difference in the energies of the two molecules. The heat
of combustion of crystalline naphthalene is ᎑1232.4 kcal/mol
and that of crystalline azulene is ᎑1264.5 kcal/mol. Azulene
has the larger (more negative) heat of combustion and is
therefore the higher-energy (less stable) isomer (5). The
difference in heats of combustion, ᎑32.1 kcal/mol, could be
thought of as the enthalpy change for the isomerization of
solid azulene to solid naphthalene. Notice that the relative
difference in enthalpies of combustion is only 2.5%. A new
semimicro bomb calorimeter makes the measurement of this
rather small energy difference possible in the undergraduate
laboratory; recent developments in electronic structure theory
permit accurate calculation of this energy difference on fast,
affordable microcomputers.
1341
Information • Textbooks • Media • Resources

Experimental Bomb Calorimetry Table 1. Experimental Enthalpy of Combustion,

⌬ H/ kcal mol –1
The Parr 1425 Semimicro Calorimeter, introduced about
W/O Wire W/ Wire
six years ago, uses the 1107 (22-mL) oxygen bomb. (With a C10H8 Isomer Literatureb
Correction Correctiona
conversion kit sold by Parr, this bomb can be used inside the
Naphthalene ᎑1236.8 (4.7) ᎑1232.3 (4.4) ᎑1232.4
well-known Parr solution calorimeter.) The bomb’s small size
makes it safer and easier to handle than the traditional 1108 Azulene ᎑1270.1 (5.4) ᎑1266.5 (5.4) ᎑1264.5
“bucket” (342-mL) bomb. In addition, the 1107 bomb Difference ᎑33.3 (7.2) ᎑34.2 (7.0) ᎑32.1
handles samples of 200 mg or less, about one-tenth the sample
NOTE: Values are the average of three student trials, corrected for
size required by the 1108 bomb. The smaller sample size constant-volume combustion. Standard deviation is in parentheses.
opens up the possibility of experiments on materials that are aAssuming an average wire burn of 5 cm at 2.3 cal/cm. Applied to

either too expensive or too energetic for the larger bomb. We
exploit this feature to measure the heat of combustion of
azulene. Azulene’s current price is $97 per gram (Aldrich
1995) and it is sold in 1-g amounts only. Since the sample
size in a 1108 bomb is 1–2 g, azulene is too expensive for
the usual undergraduate bomb. The semimicro bomb permits
determinations using just 100 mg of azulene; thus the “price
per burn” drops to $10, and 1 g of material will serve for
roughly ten trials. (As an alternative to purchasing azulene,
it can be synthesized using a procedure previously published
in this Journal [6 ]. This preparation is suitable for under-
graduate students.)
Standardization trials using benzoic acid pellets should
be performed as described in the Parr manual to determine
the heat capacity of the calorimeter. The mass of water in
the Dewar should be the same from one trial to the next.
With 450 g of water in the Dewar the heat capacity of the
semimicro calorimeter will be about 530 cal/°C (2220 J/°C);
under these conditions burning the benzoic acid pellets will
produce a 2.5 °C temperature rise.
Avoid the common “organic lab”-grade 98% naphthalene;
it produces inconsistent results. We used 99% naphthalene
and 99% azulene from Aldrich without further purification.
Pellets of naphthalene and azulene can be made using the
pellet press and small die sold by Parr. The mass of the pellets
should be at least 100 mg but should never exceed 120 mg.
Pellet masses must be measured on the highest-resolution bal-
ance available: 0.01 mg resolution is strongly recommended.
The bomb should be filled with 25 atm of oxygen to avoid
sooty burns. (The nichrome fuse wire provided by Parr will
burn and produce small beads of oxide. This is perfectly
normal and should not be taken as evidence of incomplete
combustion.) Burning these pellets will produce a tempera-
ture rise of 1.7–1.9 °C.
Table 1 presents results obtained by Moravian College
students during 1997. It shows that students can obtain ex-
cellent results. The trials can be corrected for the combus-
tion of the fuse wire: each cm of wire releases 2.3 cal of heat.
This correction, if made, should be applied to the standard-
izations with benzoic acid as well as to the trials with azulene
and naphthalene. The heat released by combustion of the fuse
wire will be about 10–13 cal/trial, typically about 1% of the
total heat liberated. (For nichrome wire there is no correc-
tion for electrical heating.) Table 1 shows that the wire cor-
rection improves the accuracy of the individual heats of com-
bustion but is not crucial for obtaining a good difference in
the heats of combustion. The calibration trials using benzoic
acid and the experimental trials on naphthalene and azulene
were also corrected for constant-volume combustion. This
correction is ∆H = ∆U + ∆ngRT, where ∆ng is the change in
the number of moles of gas due to the combustion reaction.
benzoic acid calibration trials and trials on naphthalene and azulene.
bValue for crystal ( 5).
Table 2. Calculated Electronic and Thermal Energies for
Gas Phase at 300 K, kcal/mol
C10H8 Isomer Eelec Etrans Erot Evib Etotal
Naphthalene ᎑242149.95 0.89 0.89 93.25 ᎑242054.91
Azulene ᎑242115.94 0.89 0.89 91.36 ᎑242022.79
᎑34.00 ᎑1.89 ᎑32.11
∆E 0.00 0.00
NOTE: B3LYP/6-31G(D)//RHF/6-31G(D) model of theory described
in text.
For benzoic acid ∆ng = ᎑1/2, so the correction is only ᎑0.3
kcal/mole at 25 °C; for naphthalene and azulene ∆ng = ᎑2
and the correction is ᎑1.2 kcal/mole. Although they are small,
it is pedagogically desirable to make these corrections.
Standard deviations in the heat of combustion and the
energy difference are reported to indicate the reproducibility
of the experiment. The errors in the mean values as measured
by either the standard deviation of the mean (standard error) or
95% confidence limits are slightly smaller and could be made
smaller still by increasing the number of trials. When t tests are
applied to the data, with or without the wire correction, results
indicate a >99% chance that the means of the two sets of data
are different. With minimal effort and minimal amounts of
azulene, good experimental agreement with the literature can
be obtained by students using the semimicro bomb.
Our experience indicates that consistent results depend
on consistently filling the bomb to a presure of 25 atm. Under-
filling occasionally leads to sooty burns, which must be rejected,
and a sooty azulene burn is an economic tragedy. Parr has
engineered a simple and clever solution to filling this palm-
sized bomb, but its mechanism is not obvious to undergradu-
ates who have had no experience with O-ring seals. We have
found it helpful to have each student perform a “dry run”,
assembling and sealing the bomb without wire or pellet, pres-
surizing it to 25 atm, releasing the pressure, and taking it
apart. This lessens their anxiety about filling the bomb with
oxygen, lets them see how the O-rings make seals, and gives the
instructor an opportunity to impress on them the importance
of filling to the right pressure.
Electronic Structure Calculations Using Gaussian 94
Solving Schrödinger’s equation for molecules the size of
naphthalene and azulene has always been a difficult task. Typi-
cally the Hückel approximation is used to treat large aromatic
molecules, but this approach limits the calculation to a de-
scription of the π structure of the molecule and invokes some

1342 Journal of Chemical Education • Vol. 75 No. 10 October 1998 • JChemEd.chem.wisc.edu

 Information • Textbooks • Media • Resources
serious assumptions about the resonance and overlap integrals
among the interacting π orbitals. Most students and instructors
will view the Hückel method as a gross oversimplification,
but it is still a useful point of departure for discussing naph-
thalene and azulene. Simple Hückel calculations yield the
following energies for the π-electronic structure of naphthalene
and azulene (7 ):
Naphthalene Eπ = 10α + 13.6832β
Azulene Eπ = 10α + 13.3635β
∆ Eπ = 0.3197β
Using a β value of ᎑32 kcal/mole, the difference in energy
between the two isomers is ᎑11 kcal/mol. Hückel theory yields
a correct qualitative result, but clearly a more sophisticated
model will be needed to accurately reproduce the experimental
energy difference.
Complete-electron calculations treating both the σ and
π structure of these molecules are more satisfying, and such
calculations are now possible on 486 or Pentium microcom-
puters. We will use Gaussian 94 (8), available for PC Windows
or Unix workstations, to compute the energies of naphthalene
and azulene. The theoretical models available in Gaussian
94 are still not exact solutions to the equations of quantum
mechanics, but their accuracy is sufficient to reproduce many
experimental heats of reaction. Comparisons of the results
for these models with known thermodynamic data show that
they are reliable predictive tools. For an overview of these
models, their approximations and successes, consult references
9–11. Reference 11 is especially aimed at the beginner, while
9 and 10 provide more detail.
Based on its success in predicting accurate enthalpy
changes for reactions (see ref 9), the following ab initio model
is recommended for the calculation of the energy difference.
First, the geometry of each molecule is optimized at the
RHF/6-31G(D) level, and the frequencies of vibration of each
molecule (required for the computation of the thermal energy
at 300 K) should be determined at this level. To accurately
compute the electronic energy difference between naphthalene
and azulene, our model must include some electron correlation:
the Becke3LYP model (hereafter abbreviated B3LYP), a hybrid
form of density functional theory, serves this purpose. It
is possible, but not necessary, to perform the geometry opti-
mizations and frequency calculations at the B3LYP/6-31G(D)
level. Instead, a second calculation using the B3LYP/6-31G(D)
model on the RHF/6-31G(D) optimized structures will yield
adequate results. This type of calculation is called a “single-
point calculation” because it is invoked on a fixed structure
without further geometry optimization. The electronic energies
found from the B3LYP/6-31G(D) single-point calculations
are then added to the thermal energies computed from the
RHF/6-31G(D) frequencies. The results are the total ener-
gies of naphthalene and azulene at 300 K. Results using this
theoretical model are presented in Table 2. Gaussian input
files for the required calculations on naphthalene and azulene
are listed in the Appendix.
Note the excellent agreement of the theoretical energy
difference with the experimental difference found by bomb
calorimetry. Actually, it is fortuitous that the theoretical energy
difference matches the literature value of ᎑32.1 kcal/mole—
the electronic structure calculations actually predict the gas-
phase energy difference, not the energy difference of the crystal
JChemEd.chem.wisc.edu • Vol. 75 No. 10 October 1998 • Journal of Chemical Education
Table 3. Energies Calculated Using Various Theoretical
Models at 300 K, kcal/mol
Model [ref] Naphthalene Azulene ∆H
AM1 140.31 182.70 ᎑42.40
HF/6-31G(D) ᎑240463.89 ᎑240420.69 ᎑43.20
B3LYP/6-31G(D) ᎑242056.02 ᎑242022.36 ᎑33.65
B3LYP/6-311++G(D,P) ᎑242116.42 ᎑242083.27 ᎑33.15
CBS-4/CBS-Q [12] – – ᎑35.2± 1.0
Experimental [13, 14] – – ᎑35.3± 2.2
NOTE: Energies include both the electronic and thermal energy.
Geometries were obtained by energy minimization at the stated level
of theory.
phase. Nonetheless, students should be very pleased with the
superb quantitative agreement between theory and experiment.
The contributions of different types of energy to the
overall energy difference can be determined directly from the
Gaussian output files. It is a valuable exercise for students to
summarize the results of the theoretical calculations in a table
like Table 2. Students can see that energy difference between
the isomers is dominated by the electronic component, but also
that the difference in the vibrational energy between the two
isomers does account for 6% of the computed energy differ-
ence. They can also see that the translational and rotational
components of thermal energy are equal for both isomers,
and they can verify that these correspond to the classical value
given by 1.5 RT.
The time required for these calculations is reasonable. The
calculation on azulene requires about 9 hours on a Silicon
Graphics Indy R5000 workstation. The naphthalene job is a
bit shorter (5.5 h) because of symmetry. A Pentium 90 pro-
cessor would take 4–5 times longer. This means the jobs could
not be run during a lab period, but each job could be finished
by leaving a microcomputer running over a weekend.
In the meantime, students can perform both semiempiri-
cal and other ab initio molecular orbital calculations to see
how the theoretical results compare from one level of theory
to the next and to determine what level of theory is needed
to obtain the accuracy of the calorimeter. The results of such
a study are summarized in Table 3. For each theoretical model
shown in Table 3 a complete geometry optimization has been
performed on the two molecules. The AM1 model has been
parameterized by matching heats of formation for standard
organic molecules, so it is close to the correct value but is a
little high owing to the unusual bonding characteristics of
azulene. Hartree–Fock (HF) theory using a 6-31G(D) basis
set is not much of an improvement because it still neglects
electron correlation. Density functional theory is the closest
to experiment, since it corrects for some of the effects of
electron correlation. We can see that the theory has converged
with respect to basis set, since the larger 6-311++G(D,P) basis
set leads to an answer that is not significantly different from
the one obtained at 6-31G(D). Optimizing the geometry at
the B3LYP/6-31G(D) level improves the results slightly over
the single-point method used in Table 2, but it may not be
worth the increase in computational time.
Also listed in Table 3 are the results from a family of
highly accurate models that use the complete basis set method
(CBS) (12). These are presented with error bars because there
is a range of results depending on which variant of the method
1343
Information • Textbooks • Media • Resources

one chooses. These models have extremely good agreement Discussion

with experiment. The experimental value listed in Table 3 is
for the gas phase enthalpy difference between the two isomers
at 300 K (13, 14); note that this difference is slightly higher
than the crystal difference given above. (The crystal structure
of azulene actually stabilizes azulene slightly with respect to
naphthalene, presumably because the dipole moment of
azulene yields a higher lattice energy.) It is remarkable that
theory has achieved a level of accuracy rivaling experimental
determinations of these quantities.
Students should realize that the energy difference between
the ground states of naphthalene and azulene can be accurately
measured and, with a sufficient level of theory, accurately
calculated. The calculated energy difference using the recom-
mended theoretical model falls inside the error limits of the
difference measured by bomb calorimetry. In the end, the
calculations available to students through Gaussian are more
accurate than the Parr calorimeter.

Gaussian Input Files for Naphthalene and Azulene Using the B3LYP/6-31G(D)//HF/6-31G(D) Model Chemistry

Gaussian Input File for Gaussian Input File for Explanation

Explanation Azulene
Naphthalene
%Chk=naphthalene checkpoint filename %Chk=azulene checkpoint filename
#p HF 6-31G(D) FOPT FREQ route section #p HF 6-31G(D) FOPT FREQ route section
=ReadIsotopes =ReadIsotopes
<blank line> <blank line>
Naphthalene title Azulene title
<blank line> <blank line>
01 charge and 01 charge and
C 0 0 0.7 multiplicity specifi- C 0 0 2.7 multiplicity specifi-
C 0 0 ᎑0.7 cation of atomic C 0 0 ᎑2.5 cation of atomic
C 0 2.4 ᎑0.7 coordinates in C 0 ᎑1.2 1.9 coordinates in
C 0 1.2 ᎑1.4 Angstroms C 0 1.2 1.9 Angstroms
C 0 ᎑2.4 ᎑0.7 C 0 ᎑0.7 0.5
C 0 ᎑1.2 ᎑1.4 C 0 0.7 0.5
C 0 1.2 1.4 C 0 ᎑1.6 ᎑-0.5
C 0 2.4 0.7 C 0 1.6 ᎑0.5
C 0 ᎑1.2 1.4 C 0 ᎑1.3 ᎑1.9
C 0 ᎑2.4 0.7 C 0 1.3 ᎑1.9
H 0 3.4 ᎑1.2 H 0 0 3.8
H 0 1.2 ᎑2.5 H 0 0 ᎑3.6
H 0 ᎑3.4 ᎑1.2 H 0 ᎑2.2 2.2
H 0 ᎑1.2 ᎑2.5 H 0 2.2 2.2
H 0 3.4 1.2 H 0 ᎑2.7 ᎑0.3
H 0 1.2 2.5 H 0 2.7 ᎑0.3
H 0 ᎑1.2 2.5 H 0 ᎑2.1 ᎑2.6
H 0 ᎑3.4 1.2 H 0 2.1 ᎑2.6

Temp Pressure Temp Pressure

300 1.0 0.9135 300 1.0 0.9135
Scale Scale
12 Isotope of atom 1 12 Isotope of atom 1
12 Isotope of atom 2 12 Isotope of atom 2
12 etc. 12 etc.
12 12
12 12
12 12
12 12
12 12
12 12
12 12
1 1
1 1
1 1
1 1
1 1
1 1
1 1
1 1
<blank line> <blank line>
—link1— Second Job Marker —link1— Second Job Marker
%Chk=naphthalene checkpoint filename %Chk=azulene checkpoint filename
#p B3LYP 6-31G(D) Geom #p B3LYP 6-31G(D) Geom
route section route section
=Checkpoint =Checkpoint
<blank line> <blank line>
Naphthalene title Azulene title
<blank line> <blank line>
charge and charge and
01 0 1
multiplicity multiplicity
<blank line> <blank line>

1344 Journal of Chemical Education • Vol. 75 No. 10 October 1998 • JChemEd.chem.wisc.edu

 Information • Textbooks • Media • Resources
An interesting way to implement the experiment in a
traditional two-semester physical chemistry sequence is to
carry out the bomb calorimetry experiments in the first
semester when thermodynamics is discussed and then revisit
the problem during the second semester, when quantum
chemistry is usually covered. In this way the experiment
provides a context for launching into the realm of ab initio
molecular orbital theory, the level of theory needed to under-
stand the difference observed in the first semester experiment.
As an extension of the experiment students can compute
other isomers of C10H8 and predict heats of combustion for
these molecules. A prediction of the properties of guaiazulene,
a natural product containing the azulene system, is another
possible extension.
Finally, although we recommend this experiment for the
physical chemistry lab, its application is not limited to physical
chemistry. It would be a logical extension to the synthesis
of azulene in an advanced synthesis laboratory or advanced
organic chemistry course. Other properties of naphthalene
and azulene could be the subject of experimental and theo-
retical comparison. In subsequent papers we plan to outline
lab exercises on the IR, UV–vis, and 13C NMR spectra of the
two compounds as well as a study on the site of electrophilic
aromatic substitution.
Acknowledgments
We would like to thank Gaussian, Inc., for its generous
support of this work. CS would like to thank Tom Tingle of
the Parr Instrument Company for helpful discussions.
Literature Cited
1. Shoemaker, D. P.; Garland, C. W.; Nibler, J. W. Experiments in
Physical Chemistry, 6th ed.; McGraw-Hill: New York, 1996; p 378.
Bahnick, D. A. J. Chem. Educ. 1994, 71, 171.
2. Williams, D. L.; Minarik, P. R.; Nibler, J. W. J. Chem. Educ. 1996,
73, 608.
3. Schaad, L. J.; Hess, B. A. J. Chem. Educ. 1974, 51, 640.
4. Sime, R. J.; Physical Chemistry: Methods, Techniques, and Experi-
ments; Saunders: Philadelphia, 1990; p 440. Pickering, M. J.
Chem. Educ. 1982, 59, 318.
5. CRC Handbook, 73rd ed.; Lide, D. R., Ed.; CRC: Boca Raton,
1992–93; p 5-90.
6. Lemal, D. M.; Goldman, G. D. J. Chem. Educ. 1988, 65, 923.
For a microscale version of this synthesis, see Brieger, G. J. Chem.
Educ. 1992, 69, A262.
7. Lowe, J. P. Quantum Chemistry; Academic: Boston, 1993.
JChemEd.chem.wisc.edu • Vol. 75 No. 10 October 1998 • Journal of Chemical Education
8. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.;
Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.;
Petersson, G. A.; Montgomery, J. A.; Raghavachari, K; Al-Laham,
M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski,
J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C.
Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle,
E. S.; Bomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.;
Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.;
Gonzalez, C.; Pople, J. A. Gaussian 94, Rev. D.3; Gaussian, Inc:
Pittsburgh, PA, 1995.
9. Foresman, J. B.; Frisch, A. E. Exploring Chemistry with Electronic
Structure Methods, 2nd ed.; Gaussian, Inc.: Pittsburgh, PA, 1996.
10. Hehre, W. J.; Radom, L; Schleyer, P. v. R.; Pople, J. A. Ab Initio
Molecular Orbital Theory; Wiley: New York, 1986.
11. Foresman, J. B. In What Every Chemist Should Know About Com-
puters; Swift, M. L., Zielinski, T. J., Eds.; ACS Books: Washing-
ton, DC, 1997; Chapter 14.
12. Ochterski, J. W.; Petersson, G. A.; Montgomery, J. A., Jr. J. Chem.
Phys. 1996, 104, 2598.
13. Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin,
R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1988, 17(Suppl.
1).
14. Cox, J. D.; Pilcher, G. Thermochemistry of Organic and Organo-
metallic Compounds, Academic: New York, 1970.
Appendix
Gaussian Input Files for Naphthalene and Azulene Using the
B3LYP/6-31G(D)//HF/6-31G(D) Model Chemistry
The input files on page 1344 will perform a geometry op-
timization and vibrational analysis at RHF/6-31G(D) and then au-
tomatically perform a single-point energy calculation at B3LYP/6-
31G(D) using the RHF/6-31G(D) optimized structure. Thus it will
perform the two required Gaussian calculations as a single task.
The required input files can be created using any standard
molecular sketching program (such as HyperChem or PCModel) by
making the graphics program output a file containing the Cartesian
coordinates of the atoms. Then the other job information can be
entered by using an ASCII text editor. The scale factor of 0.9135
appears in the input because this is the recommended value to account
for systematic errors in the theory at this level (determined by
comparing to a wide variety of experimental thermal energies).
It should be noted that the input file for azulene forces the
molecule to have C 2ν symmetry. Some molecular sketching pro-
grams may not provide the same symmetry; computational results may
be slightly different if the molecule relaxes to a lower symmetry. In
fact, this relaxation will happen at the level of theory used here
(indicated by the presence of one imaginary frequency in the output
file). This distortion is an artifact of the theory and results in only
a minor difference in computed energies.
1345