Journal of Hazardous Materials 164 (2009) 15521555

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Journal of Hazardous Materials

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Short communication

Density functional calculations on the thermodynamic properties of a series

of nitrosocubanes having the formula C8 H8x (NO)x (x = 1 8)
Ryan M. Richard, David W. Ball
Department of Chemistry, Cleveland State University, 2121 Euclid Avenue, Cleveland, OH 44115, USA

a r t i c l e i n f o a b s t r a c t

Article history: Recent studies have suggested that octanitrocubane and heptanitrocubane may be two of the most pow-
Received 16 May 2008 erful non-nuclear high-energy materials currently known. Progressive substitution of the hydrogen atoms
Received in revised form 5 August 2008 on cubane for nitroso groups is expected to also produce a new potential high-energy material, which
Accepted 6 August 2008
should have thermodynamic properties similar to nitrocubane. In this study we predict optimized struc-
Available online 26 August 2008
tures, vibrational frequencies, enthalpies of formation, and specic enthalpies of combustion for a series of
nitrosocubanes ranging from mononitrosocubane to octanitrosocubane. Our results indicate, on the basis
Keywords:
of the specic enthalpies of combustion alone, that mononitrosocubane should make the best new high-
Nitrosocubanes
High-energy materials
energy material; however, we speculate that the velocity of detonation of octa- and heptanitrosocubane
B3LYP will make them better high-energy materials.
2008 Elsevier B.V. All rights reserved.

1. Introduction high-energy materials, which makes octanitrocubane and similar

Octanitrocubane was rst synthesized in 2000 in 4555% yield
from heptanitrocubane [1]. In a follow-up study, Eaton et al. [2]
described the properties of octanitrocubane and heptanitrocubane
in relation to current high-energy materials. This study listed the
density of octanitrocubane to be 1.982.06 g/cm3 , as it depends
on the exact orientation of the nitro groups and the presence of
water of hydration. Because the velocity of detonation is linearly
related to the density, denser molecules have faster velocities of
detonation and are overall better explosives. Strain energy of the
cubane skeleton is also expected to raise the energy output of these
materials.
Octanitrocubane is also an appealing high-energy material
because of the way the nitro group attaches to the cubane structure,
via a CN bond. Eaton et al. [2] make the conjecture that a CNO2
bond, because of its relative strength, will make nitrocubanes more
insensitive to shock as opposed to the ONO2 bond, which is rel-
atively weaker and is found in shock sensitive explosives such
as nitroglycerin. Eaton et al. [3] conrmed that octanitrocubane
and heptanitrocubane are shock insensitive by hitting the com-
pounds repeatedly with a hammer and not achieving detonation. A
recent review [4] of advances in high-energy materials has stated
that research efforts are currently concerted on making insensitive
Corresponding author.
E-mail address: d.ball@csuohio.edu (D.W. Ball).
compounds all the more interesting.
Studies have shown that other nitrogen-containing functional
groups can also lead to a molecule being a good potential high-
energy material [5]. Another nitrogen-containing functional group,
and the one we are interested in for this study, is the nitroso
group. The main noticeable difference between a nitro group and
a nitroso group is the oxygen content of the group. Upon com-
plete combustion, carbon forms CO2 ; this means that the nitro
group has the advantage of containing stoichiometrically the right
amount of oxygen for complete combustion of the carbon it is
attached to. The nitroso group, on the other hand, contains half
of the required oxygen. In an oxygen rich environment, such
as Earths atmosphere, this should not be a problem, although
additional oxidizer may be necessary to promote complete oxidiza-
tion.
A literature search on nitrosocubanes failed to yield any previ-
ous work on the topic, leading us to conclude that this is the rst
time these systems have been considered. However, we were able
to locate a comparable study by Gejji et al. [6] done on the entire
series of nitrocubanes and will use this as a comparison study.
Other substituents, like NH2 [7], and diazo groups [8], have also
been explored as cubane modiers. Dhumal et al. [9,10] studied
the effects of substituting the carbons in various nitrocubanes for
nitrogen atoms; their results indicate that the enthalpies of forma-
tion get progressively larger as the number of nitrogen atoms in the
cubane structure increase, culminating at an enthalpy of formation
of 1954.8 kJ/mol for octaazacubane.

0304-3894/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2008.08.057
 R.M. Richard, D.W. Ball / Journal of Hazardous Materials 164 (2009) 15521555 1553

2. Computational details

All calculations were performed on either a personal com-

puter or the Itanium Cluster at the Ohio Supercomputer Center
(OSC) using Gaussian 03 [11]. Structures were optimized and vibra-
tional frequencies were determined using Beckes three-parameter
exchange functional with Lee et al. correlation functional (B3LYP)
[12,13]. All calculations were done using the internally stored 6-
311G (d, p) basis set and assuming the molecules were in singlet
states in the ground state. In order to not preclude any possible
minimum energy structures, the molecules symmetries were not
constrained. Structures and vibrational frequencies were visual-
ized using the GaussView Program [14]. Vibrational spectra were
generated using the SWizard program [15].
Calculation of the enthalpy of formation was accomplished by
use of the isodesmic reaction listed as follows:

C8 H8x (NO)x (g) + xCH4 (g) xCH3 NO (g) + C8 H8 (g) (1)

Enthalpies of formation for methane, nitrosomethane, and

cubane were obtained from the National Institute of Standards
and Technologies (NIST) Chemistry Webbook Website [16]. Respec-
tively, these values are: 74.9, 66.9, and 622.2 kJ/mol. Using the
enthalpy of formation of the nitrosocubane obtained from Reac-
tion (1) it is a straightforward process to determine the enthalpy of
combustion using Reaction (2):
C8 H8x (NO)x (g) + 0.5(20 1.5x)O2 (g) 8CO2 (g)
+ 0.5(8 x)H2 O (l) + 0.5xN2 (g)
Enthalpies of formation for carbon dioxide and water were also
obtained from the NIST Chemistry Webbook website [16]; these
values are 393.52 and 285.83 kJ/mol, respectively. In Reaction
(2), we are assuming complete oxidation of carbon to carbon diox-
ide, rather than partial oxidation to carbon monoxide, as suggested
by the modied Kistiakowsky-Wilson rules [17] because we believe
that a complete combustion reaction serves as a better benchmark
for comparison among substances. Dividing the enthalpies of com-
bustion by the molecular mass yields the specic enthalpies of
combustion, which gives the energy released upon combustion as
a function of mass.
Fig. 1. Numbering scheme for substitute cubanes.
optimized geometries of the 21 isomers is not warranted, as the
structures are what one would predict based on chemical intuition
alone.
Fig. 2 shows the optimized geometry for octanitrosocubane; we
choose to depict octanitrosocubane because it is the most likely
(2)
candidate for a new high-energy material, based on analogy to
octanitrocubane. As expected, the geometry exhibits a pinwheel
sort of orientation, in the sense that each nitroso group points to
another nitroso group. A computational study by Hrovat et al. [18]
of octanitrocubane at the restricted Hartree-Fock (RHF) and B3LYP
levels of theory concluded that octanitrocubanes minimum energy
geometry was not the one having the highest symmetry, but the
one that minimizes oxygenoxygen repulsion between two adja-
cent nitro groups, which is also a pinwheel structure. It is also fairly
apparent from Fig. 2 that the central cubane structure is skewed in
the sense that is not a perfect cube. Octanitrosocubane is predicted

3. Results and discussion

3.1. Optimized geometries

Fig. 1 shows the numbering scheme for cubane derivatives. The

numbering system was used such that the numbers labeling the
nitroso groups are the smallest numbers possible and still con-
sistent with the numbering pattern shown in Fig. 1. There are a
total of 21 structural isomers, and the Cartesian coordinates of
the optimized geometries of these 21 isomers are available as
Supplementary material. It should also be mentioned at this time
that many additional stereoisomers exist that were not considered
here. Each nitroso group could essentially exist in either an up or
down conguration with respect to a side of the cube. What this
means is that for each structural isomer 2n stereoisomers exist,
with n being the number of nitroso groups present. This of course
does not eliminate stereoisomers that are the same from symmetry
considerations. When designing input structures, we attempted to
minimize steric effects, producing what we hope are the minimum
energy stereoisomer for each structural isomer. These structures
have not been conrmed to be the absolute energy minima struc-
tures, and should at the very least be taken as being representative
of the structural isomer they represent. A lengthy discussion of the Fig. 2. Optimized geometry of octanitrosocubane.
1554 R.M. Richard, D.W. Ball / Journal of Hazardous Materials 164 (2009) 15521555

Fig. 3. Predicted vibrational spectrum for octanitrosocubane.

to have essentially no dipole moment, although its experimental The third and fourth columns of Table 1 list the predicted
dipole moment may depend on the relative orientations of the enthalpies of formation and the specic enthalpies of combus-
nitroso groups. tion of the series of nitrosocubane molecules. Two benchmarks for
our discussion of the enthalpies of formation (the second numer-
ical column of Table 1) are the enthalpy of formation of cubane,
3.2. Vibrational spectra
which is 622 kJ/mol [16], and the enthalpy of formation of octan-
itrocubane, which is 649.8 kJ/mol [6]. Interesting enough, both of
Predicted vibrational frequencies were computed for all
these benchmark molecules are thermodynamically unstable than
molecules and the resulting unscaled vibrational spectra were
any of the isomers considered here. Octanitrosocubane and hep-
included as part of the calculations. Plots of the calculated vibra-
tanitrosocubane have roughly the same enthalpy of formation, and
tional spectra are available as Supplementary material. As an
are the least thermodynamically stable molecules in our study.
example of what the vibrational spectra look like, we have included
They are, however, more stable than cubane and octanitrocubane
the vibrational spectra of octanitrosocubane, which is shown here
by about 20 and 50 kJ/mol, respectively.
as Fig. 3. We choose octanitrosocubane for the same reason given
The instability is least in the tetranitrosocubane series with
above. This particular vibrational spectrum stands out in that
1,3,5,7-tetranitrosocubane, which has the lowest enthalpy of for-
because there are no more CH bonds in octanitrosocubane, the
mation of the molecules studied here. Gejji et al. [4] report a similar
CH stretching and bending regions of the spectrum are blank,
pattern in the enthalpies of formation of the nitrocubane series
while in the lesser-substituted nitrosocubanes there are some
with 1,3,5,7-tetranitrocubane isomer having the lowest enthalpy
absorptions in those ranges. Determination of the isomers based
of formation. Eaton et al. [2] discussed the difculty in nitrating
on their spectra alone is complicated by the fact that many of the
cubane beyond four nitro groups, which is in excellent agreement
spectra are fairly similar with subtle differences in the ngerprint
region of the spectra. Careful spectral interpretation can lead to
these spectra proving useful in aiding in identication of the various Table 1
Enthalpies of reaction
structural isomers when they are synthesized.
Molecule OB% Hf (kJ/mol) Hc (kJ/g)

3.3. Energies of reaction Mononitrosocubane 223 593.6 35.7

1,2-Dinitrosocubane 168 590.2 28.4
1,3-Dinitrosocubane 168 572.9 28.3
Table 1 lists the various nitrosocubane molecules studied here. 1,8-Dinitrosocubane 168 572.0 28.3
The rst numerical column in Table 1 is the oxygen balance for each 1,2,3-Trinitrosocubane 130 569.5 23.2
formula. The oxygen balance (OB%) of substances containing only 1,2,5-Trinitrosocubane 130 563.0 23.2
1,3,5-Trinitrosocubane 130 559.0 23.2
carbon, hydrogen, nitrogen, and oxygen is dened as
1,2,3,4-Tetranitrosocubane 102 572.1 19.5

1600
 y
 1,2,3,5-Tetranitrosocubane 102 560.5 19.5
OB% = z 2x (3) 1,2,3,6-Tetranitrosocubane 102 562.8 19.5
molar mass of compound 2 1,2,3,7-Tetranitrosocubane 102 569.1 19.5
1,2,5,8-Tetranitrosocubane 102 561.8 19.5
where the variables x, y, and z in Eq. (3) come from the subscripts 1,3,5,7-Tetranitrosocubane 102 552.6 19.4
in the general formula of the substance when written as Cx Hy Nw Oz 1,2,3,4,5-Pentanitrosocubane 80 574.4 16.7
[19]. All of the nitrosocubane molecules have a negative oxygen 1,2,3,5,6-Pentanitrosocubane 80 567.7 16.6
1,2,3,5,7-Pentanitrosocubane 80 560.4 16.6
balance, indicating that additional oxygen is needed to promote 1,2,3,4,5,6-Hexanitrosocubane 63 584.4 14.5
complete combustion. This should not be surprising, as we noted 1,2,3,4,6,8-Hexanitrosocubane 63 580.7 14.4
in the Introduction that octanitrocubane has the correct formula for 1,2,3,5,6,8-Hexanitrosocubane 63 577.7 14.4
complete oxidation without additional oxygen, i.e. octanitrocubane Heptanitrosocubane 50 599.1 12.7
Octanitrosocubane 38 599.3 11.2
has an oxygen balance of zero.
 R.M. Richard, D.W. Ball / Journal of Hazardous Materials 164 (2009) 15521555
with our predicted pattern and Gejji et al. [6] predicted pattern.
Thus, the apparent trend in energies does not follow the trend in
oxygen balance.
The nitroso group is an electron-withdrawing group. As the
number of nitroso groups on the cubane framework increases,
two opposing factors are at play here: increasing the amount of
electron withdrawal and the steric hindrance resulting from the
additional functional group. Eight functional groups would repre-
sent the maximum amount of electron withdrawal possible, but the
energy gained from steric hindrance causes the molecule to be more
unstable then if it were to have fewer groups present. The maxi-
mum gain in stability occurs at four functional groups arranged in
the 1,3,5,7-substituted, which also puts the nitroso groups in the
least hindered, tetrahedral positions (Fig. 1).
The third numerical column in Table 1 shows the specic
enthalpies of combustion, which is the molar enthalpy of com-
bustion divided by the molar mass of the substance. The general
trend is that an increase in number of nitroso groups leads to less
energy given off per unit mass upon combustion. This is due to
the fact that we are replacing hydrogen atoms, each of which con-
tributes to roughly 142.5 kJ/mol or about 8 kJ/g of energy upon
combustion by forming water. Steric hindrance compensates for
some of the lost 8 kJ/g, but not enough to make an additional
nitroso group cause the molecule to give off more energy than it
did when it had one less nitroso group. However, it is interesting
to point out that octanitrocubane only gives off 8.2 kJ/g of energy,
making it still less than any of the molecules considered here.
Thus, based on the specic enthalpy of combustion alone, octani-
trosocubane seems to be a better high-energy material than its nitro
counterpart.
Ultimately, the usefulness of any of the nitrosocubanes as
high-energy materials is going to depend on their velocities of deto-
nation, which is primarily a function of their densities, where higher
density produces a faster velocity of detonation. Comparing octan-
itrocubane to octanitrosocubane, it is apparent that nitrocubane
has the mass advantage, as each nitro group contains 16 amu more
mass than a nitroso group. If both have a relatively similar molar
volume, than octanitrocubane will have a higher density and thus
make a better high-energy material. The nitroso functional group
does take up less volume than a nitro group, so it is possible that
despite the lower molar mass, nitrosocubanes may have a higher
density than the corresponding nitrocubane. Given the difculty in
the synthesis of octanitrocubane, octanitrosocubane may still prove
to be a viable candidate for a new high-energy material, provided
it can be synthesized easier.
4. Conclusion
We have presented here the rst study on a series of
nitrosocubanes, which have the potential to be new high-energy
materials. We have predicted enthalpies of formation and specic
enthalpies of combustion, as well as vibrational spectra and opti-
mized geometries. These results should be representative of the
respective structural isomers, but slight differences will occur due
to different stereoisomers. Based on our results octanitrosocubane
will give off more energy than octanitrocubane when combusted;
however, we have also cautioned that the true usefulness of these
high-energy materials will be dependent on their velocities of com-
bustion and predict that octanitrocubane will be better in that
regard. Given the difculty in synthesizing octanitrocubane, octan-
1555
itrosocubane may prove to be a viable alternative high-energy
material, provided it can be synthesized easier.
Acknowledgements
The authors wish to express their gratitude to the Ohio Super-
computer Center for their generous gift of time on the Itanium
supercomputer. Additionally, RMR wishes to express his thanks to
the Honors Program at CSU for their continuing support.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.jhazmat.2008.08.057.
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