Computational Analysis of Three Polynitroaromatic Molecules (TNT, TNB, and

TNA) and the Impact of their Nitro groups on Various Properties

Jesse Braun
The Unversity of Akron, Physical Chemistry II, Professor Michael Konopka, Dated May 15, 2015

Ab initio calculations were determined for properties of the three polynitroaromatic compounds TNT,
TNB, and TNA including bond length between nitro groups and the central carbon ring, atomic charge of
the bonding carbon with each nitro group and nitrogen, and dihedral angle of nitro groups in TNT. Both
Hartree-Fock (HF) and MP2 models were utilized in the computational analysis under varying basis sets
ranging from ST0-3G to 6-311+G** and used to compare differences in properties. The electrostatic
potential at the midpoint of each C-N bond (V_mid) was calculated from the bond length and atomic
charges and compared to experimental data of shock and impact sensitivities of the molecules, showing a
strong correlation between each.

Introduction
Quantum chemistry allows us the ability to create models of how molecules should behave,

sometimes down to extreme accuracy, and calculate various properties which can be compared to

experimental results. It is this ability that makes software like Spartan Student so valuable when

exploring new molecules or attempting to understand existing relationships better. There have been

many studies and interest in dealing with polynitroaromatic molecules for many reasons, if not mainly

due to their explosive natures like TNT. By the use of computational analysis and ab initio calculations

utilizing the Spartan Student software, better insight can be observed into why these compounds are

explosive or why very similar molecules have different sensitivities.

The experimentation done here within intended to perform ab initio calculations using Spartan

Student software of three polynitroaromatic compounds including 1,3,5-trinitrobenzene (TNB), 2,4,6-

trinitroaniline (TNA), and 2,4,6-trinitrotoluene (TNT). Images of these compounds are depicted in Figures

1-3. The goal was to compare these three molecules with varying nitro groups by analyzing various

properties including bond length between each carbon and nitro group, atomic charges of the carbon

and connected nitrogen atoms by treating each as a point charge, and using a relationship given in

(Owens, Jayasuria, Abrahamsen, & Politzer, 1985) to determine the positive potential at the center of
the C-NO2 bond. It is illustrated in that journal how this potential is well correlated with their shock

sensitivities measured for the molecules, which is an interesting characteristic to compare with these

polynitroaromatic molecules as they are explosive upon impact (as would be expected with TNT). The

dihedral angle of each Nitro group with the Carbon ring in TNT was also observed and compared.

The computations were done utilizing Spartan Student software under various quantum

mechanical models and basis sets. These included the following: Hartree-Fock (HF)_STO-3G, HF_3-21G,

HF_6-31G*, HF_6-311+G**, and MP2 Mller-Plesset_6-31G*. All five variations were used for each of

the calculations measured including bond length, atomic charge, and dihedral angle. This was done in

Spartan Student by changing the calculation method and letting the software run the simulation until

the energy change was minimized, then simply using the tools of the software to indicate the desired

property. The purpose of running all the simulations was depict the severity of how properties can

change dependent upon which model or basis set is chosen. The molecules themselves were created in

the software by using the tools to create a new molecule and naming it appropriately, as seen in Figures

1-3.

Results and Discussion

The ab initio calculations procured data for properties including bond length, dihedral angle, and

atomic charge for each of the three molecules under varying models and basis sets. A capture of each

molecule studied in the Spartan Student software including individually numbered atoms is depicted in

Figures 1-3. The bond lengths between each Nitro group and main Carbon ring were calculated and

numbered in reference to these figures, detailed in Table 1. The bond lengths were reported in

Angstroms and the average value between the three C-N bonds was calculated in order to better

visualize the variation between model and basis sets as well as varying molecules.

It is shown that the bond lengths vary steadily as basis sets are increases, however once at a

high level of modeling there is much less variation between the calculated results, such as HF_6-
311+G** and MP2_6-31G*. Even between the same basis set of 6-31G* and HF to MP2 there is visible

difference in calculated values. The bond length results also illustrate how the three molecules were

initially different under low basis sets but became very close to having the same bond lengths at high

basis sets, interpreted as a higher level of accuracy seems to imply stronger similarities between the

molecules of TNT, TNA, and TNB.

Dihedral angles were also calculated between the Nitro groups and main carbon ring of the

molecule TNT, and used to compare with experimental data found through crystalline structure analysis

taken from (Holden, Dickinson, 1972). The dihedral angle results of TNT illustrate strongly the variance

that can be seen between simulations under different models or basis sets. The experimental values

reported in (Holden, Dickinson, 1972) and detailed in Table 2 are compared to the results obtained from

this experimentation. The closest relatable values to these experimental values was obtained using

either HF_6-311+G** or MP2_6-31G*, while the lower lever basis sets under HF model significantly

deviate from the expectation values. This illustration again showcases the power of choosing the correct

quantum mechanical modeling system for the desired properties and how sensitive a property like

dihedral angle can be in a non-linear molecule to ab initio calculations.

The atomic charge of each nitrogen and carbon connecting the Nitro groups was calculated

treating each as a point charge and reporting values in electron volts. The individual atoms are

numbered according to their position in Figures 1-3 and the results are tabulated in Table 3. An

important note regarding the atomic charge values obtained is that these are the Mulliken eV values

representing large fluctuations between varying models or basis sets in the computational analysis. This

is due to the assignment of charge to the center of each atom based on the total electron density at that

center determined by the specified basis set. This partitioning is often undermined by the large spatial

extent of basis functions included in many modern basis sets (Cremer et al., 1993). It was illustrated

there how the Mulliken Populations can be extremely dependent on basis sets.
 The atomic charges calculated and listed in Table 3 illustrate another indication of the

fluctuation between basis sets and models. The large variance between each molecule shows how, even

given the strong similarities of the three, a simple change in molecular structure can impact properties

like atomic charge on each of the atoms of the molecule and affect other properties as well. It is

important that a sufficient basis set be chosen when calculating a desirable property to be compared

with experimental values, because if a low level of confidence is used large error may be associated

leading to inaccurate correlations between data or results.

From the data for bond lengths and atomic charge (Tables 1 & 3) a new parameter for the

electrostatic potential at the midpoint of each C-N bond (V_mid) was calculated using the following

equation:

= + (1)
0.5 0.5

in which R is the bond length between the carbon on the main ring and the nitrogen in each Nitro group.

Equation 1 was reported from (Owens, Jayasuria, Abrahamsen, & Politzer, 1985) and signifies the

positive potential at the midpoint between the molecules. It can be seen from Table 3 that how both the

carbon and nitrogen charges are both positive leading to this positive potential and thus instability in

the molecule itself. From this interpretation the values for V_mid can be compared with shock

sensitivity data to correlate the impact of this property on the explosive nature of the molecules. The

V_mid calculations were done using the average bond length (converted to atomic units) and the

corresponding charges (also converted to atomic units), followed by averaging the different nitro groups

per molecule to determine a final V_mid per molecule per model and basis set. These values are listed in

Table 4, as well as the conversion factors used in the calculations.

The V_mid results indicate the difference between the molecules in their stability based on

electrostatic potentials. Between each basis set there is also much variation, however this is largely due

to the atomic charge fluctuations given in Table 3. This characterization of electrostatic potential in the
C-N bonds characterizes a new and real property correlated to the explosive sensitivity of the molecules,

and the difference between the molecules illustrates how the varying molecular geometries or

compositions can affect this sensitivity.

Experimental results were taken from (Owens, Jayasuria, Abrahamsen, & Politzer, 1985) for the

shock sensitivity gap test (in inches) and impact sensitivity drop test (in cm) for the three molecules

experimented and compared to the values obtained through ab initio calculations for V_mid. These

values are listed in Table 5. The V_mid values depicted are an average of all model and basis sets

combined to get a relative trend of the three molecules. This data was then graphed and depicted in

Figures 4 & 5 illustrating the strong correlation between these V_mid values with the sensitivity data in

the explosive natures.

The results depicted in Figures 4 & 5 illustrate how TNB (being the simplest of the molecules)

shows the highest level of shock sensitivity of the three molecules. With the addition of another carbon

bonded to the ring for TNT, the shock sensitivity decreases extensively possibly due to the reduction of

the positive potential created by the Nitro groups presents. TNA shows the lowest sensitivity and may

be caused by the replacement from the added carbon in TNT to a nitrogen atom, further decreasing the

positive potentials of the Nitro groups. There is a strong correlation between the values obtained for

V_mid and the shock or impact sensitivity data, exceeding 99%, indicating the possibility of this response

value V_mid to be a real and observable property of these polynitroaromatic molecules and may lead to

further insight into why these compounds are so explosive and the reaction mechanisms that are

involved.
 Results

Figure 1: 2,4,6-trinitrotoluene (TNT) molecular

structure in ball-and-spoke model format
including number labeling for each atom as
referenced in data tables and text.

Figure 3: 2,4,6-trinitroanaline (TNA) molecular

structure in ball-and-spoke model format
including number labeling for each atom as
referenced in data tables and text.

Figure 2: 1,3,5-trinitrobenzene (TNB) molecular

structure in ball-and-spoke model format
including number labeling for each atom as
referenced in data tables and text.
Table 1: Ab initio calculations of bond length (in Angstroms) between the nitro groups and carbon ring
of TNT, TNA, and TNB under different model and basis sets, including average values. Atoms are
labeled according to their corresponding molecular structures depicted in Figures 1-3.
TNT TNB
Bond Length (A) Bond Length (A)
Model Basis
C2-N1 C4-N2 C6-N3 Average C1-N1 C3-N2 C5-N3 Average
HF STO-3G 1.515 1.506 1.515 1.512 1.509 1.509 1.509 1.509
HF 3-21G 1.459 1.433 1.459 1.450 1.447 1.447 1.447 1.447
HF 6-31G* 1.463 1.456 1.463 1.461 1.459 1.459 1.459 1.459
HF 6-311+G** 1.472 1.463 1.472 1.469 1.467 1.467 1.467 1.467
MP2 6-31G* 1.469 1.474 1.469 1.471 1.479 1.479 1.479 1.479
TNA
Bond Length (A)
Model Basis
C2-N1 C4-N2 C6-N3 Average
HF STO-3G 1.500 1.499 1.500 1.500
HF 3-21G 1.438 1.403 1.438 1.426
HF 6-31G* 1.453 1.445 1.453 1.450
HF 6-311+G** 1.472 1.466 1.472 1.470
MP2 6-31G* 1.472 1.466 1.472 1.470

Table 2: Ab initio calculations of the dihedral angle (in degrees) between the nitro groups and carbon
ring in TNT under various models and basis sets, illustrating the variance between sets. Experimental
values are also listed taken from (Holden, Dickinson, 1972) to compare with calculated values.
TNT
Dihedral ()
Model Basis
N1 N2 N3 TNT
HF STO-3G 36.48 0.36 36.48 Experimental Dihedral ()
HF 3-21G 33.4 0.36 33.4 N1 N2 N3
HF 6-31G* 35.85 0.07 35.78 55 27 44
HF 6-311+G** 47.16 0.48 47.16
MP2 6-31G* 55.67 0.59 55.11
Table 3: Ab initio calculations of atomic charges (by Mulliken Populations technique) in
electron volts, eV, of each carbon-nitrogen pairing in the molecules of TNT, TNB, and TNA
under various models and basis sets. This data illustrates the fluctuation between different
basis sets, and is also used in determining V_mid (refer to Table 4). Atoms are labeled
according to their corresponding molecular structures depicted in Figures 1-3. Experimental
values are also listed for comparison, obtained from (Owens, Jayasuria, Abrahamsen, &
Politzer, 1985).
TNT
Charge (Mulliken eV)
Model Basis
Qc-2 Qn-1 Qc-4 Qn-2 Qc-6 Qn-3
HF STO-3G 0.082 0.133 0.083 0.135 0.082 0.133
HF 3-21G 0.277 0.183 0.270 0.171 0.277 0.183
HF 6-31G* 0.117 0.491 0.131 0.526 0.117 0.491
HF 6-311+G** 0.181 -0.077 0.128 -0.071 0.181 -0.077
MP2 6-31G* 0.174 0.294 0.215 0.321 0.174 0.294
Experimental 0.092 0.177 0.105 0.173 0.094 0.172
TNB
Charge (Mulliken eV)
Model Basis
Qc-1 Qn-1 Qc-3 Qn-2 Qc-5 Qn-3
HF STO-3G 0.089 0.135 0.089 0.135 0.089 0.135
HF 3-21G 0.272 0.182 0.272 0.182 0.272 0.182
HF 6-31G* 0.128 0.532 0.128 0.532 0.128 0.532
HF 6-311+G** 0.248 -0.044 0.248 -0.044 0.248 -0.044
MP2 6-31G* 0.222 0.327 0.223 0.327 0.222 0.327
Experimental 0.092 0.190 0.092 0.172 0.092 0.190
TNA
Charge (Mulliken eV)
Model Basis
Qc-2 Qn-1 Qc-4 Qn-2 Qc-6 Qn-3
HF STO-3G 0.040 0.137 0.052 0.133 0.04 0.137
HF 3-21G 0.262 0.174 0.245 0.156 0.262 0.174
HF 6-31G* 0.085 0.540 0.103 0.529 0.085 0.54
HF 6-311+G** 0.179 -0.078 0.193 -0.076 0.179 -0.078
MP2 6-31G* 0.186 0.337 0.223 0.323 0.186 0.337
Experimental 0.055 0.176 0.068 0.171 0.052 0.178
Table 4: Ab initio calculations of the positive potential in the C-NO2 intermolecular region at the
midpoint, given by the equation V_mid = QC/0.5R + QN/0.5R (Owens, Jayasuria, Abrahamsen, &
Politzer, 1985), with R being the longest C-NO2 bond length (found in Table 1), between TNT, TNB, and
TNA at different model and basis sets. The average value for V_mid is also given to compare the
molecules, and useful conversion factors used in the calculations are also given. Atoms are labeled
according to their corresponding molecular structures depicted in Figures 1-3.
TNT TNB
V_mid (a.u.) V_mid (a.u.)
Model Basis
C2-N1 C4-N2 C6-N3 Average C1-N1 C3-N2 C5-N3 Average
HF STO-3G 0.120 0.122 0.120 0.121 0.130 0.130 0.130 0.130
HF 3-21G 0.397 0.386 0.397 0.394 0.393 0.393 0.393 0.393
HF 6-31G* 0.207 0.229 0.207 0.214 0.226 0.226 0.226 0.226
HF 6-311+G** 0.239 0.167 0.239 0.215 0.334 0.334 0.334 0.334
MP2 6-31G* 0.265 0.323 0.265 0.284 0.331 0.332 0.331 0.331
TNA
V_mid (a.u.) 1 eV = 1.6E-19 Joules
Model Basis
C2-N1 C4-N2 C6-N3 Average 1 a.u. = 4.36E-18 Joules
HF STO-3G 0.066 0.082 0.066 0.071
HF 3-21G 0.381 0.356 0.381 0.373 1 a.u. = 0.529177 Angstrom
HF 6-31G* 0.169 0.192 0.169 0.177 1 a.u. = 27.21 eV
HF 6-311+G** 0.236 0.255 0.236 0.242
MP2 6-31G* 0.285 0.333 0.285 0.301
Table 5: Experimental results obtained from (Owens, Jayasuria, Abrahamsen, & Politzer, 1985) of the
impact and shock sensitivities of the molecules TNB, TNA, and TNT as well as the average of the
calculated V_mid values from all model and basis sets listed in Table 4 for each molecule.
Impact Shock V_mid
Molecule Sensitivity Drop Sensitivity Gap (average of all ab
Test (cm) Test (in) initio calculations)
TNB 100 0.32 0.283
TNT 160 0.26 0.246
TNA 177 0.23 0.233

0.34

0.32
Shock Sensitivity Gap Test (in)

0.30

0.28

y = 1.7454x - 0.1729
0.26 R = 0.9925

0.24

0.22

0.20
0.22 0.23 0.24 0.25 0.26 0.27 0.28 0.29
V_mid (average a.u.)

Figure 4: Shock sensitivity gap test experimental data for TNT. TNB, and TNA compared to ab initio
calculations of V_mid (detailed in Table 5) showing a strong correlation between the two of 0.9925.
Experimental data was obtained from (Owens, Jayasuria, Abrahamsen, & Politzer, 1985).
 200

180
Impact Sensitivity Drop Test (cm)

160

140

120
y = -1545.5x + 537.84
R = 0.9988

100

80
0.220 0.230 0.240 0.250 0.260 0.270 0.280 0.290
V_mid (average a.u.)

Figure 5: Impact sensitivity drop test experimental data for TNT. TNB, and TNA compared to ab initio
calculations of V_mid (detailed in Table 5) showing a strong correlation between the two of 0.9988.
Experimental data was obtained from (Owens, Jayasuria, Abrahamsen, & Politzer, 1985).
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