ARL-TN-0737 ● FEB 2016

US Army Research Laboratory

Theoretical Prediction of the Heats of 

Formation, Densities, and Relative Sensitivities 

for 3,7-diamino-2,4,6,8-tetranitro-1,5-

diazanaphthalene (DATNP) and 3,7-diamino2,4,6,8-tetranitro-1,5-diazanaphthalene 1,5-Noxide (DATNPO)

by Edward FC Byrd

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Army position unless so designated by other authorized documents.

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Destroy this report when it is no longer needed. Do not return it to the originator.
ARL-TN-0737 ● FEB 2016

US Army Research Laboratory

Theoretical Prediction of the Heats of 

Formation, Densities, and Relative Sensitivities 

for 3,7-diamino-2,4,6,8-tetranitro-1,5-

diazanaphthalene (DATNP) and 3,7-diamino2,4,6,8-tetranitro-1,5-diazanaphthalene 1,5-Noxide (DATNPO)

by Edward FC Byrd

Weapons and Materials Research Directorate, ARL

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FOR OFFICIAL USE ONLY (delete if not FOUO)
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1. REPORT DATE (DD-MM-YYYY)

February 2016

2. REPORT TYPE

Technical Note

3. DATES COVERED (From - To)

1–30 September 2015

4. TITLE AND SUBTITLE

Theoretical Prediction of the Heats of Formation, Densities, and Relative 

Sensitivities for 3,7-diamino-2,4,6,8-tetranitro-1,5-diazanaphthalene (DATNP) 

and 3,7-diamino-2,4,6,8-tetranitro-1,5-diazanaphthalene 1,5-N-oxide 

(DATNPO)

5a. CONTRACT NUMBER

5b. GRANT NUMBER

5c. PROGRAM ELEMENT NUMBER

6. AUTHOR(S)

Edward FC Byrd

5d. PROJECT NUMBER

5e. TASK NUMBER

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US Army Research Laboratory

ATTN: RDRL-WML-B

Aberdeen Proving Ground, MD 21005-5069

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ARL-TN-0737

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13. SUPPLEMENTARY NOTES

14. ABSTRACT

The US Army Research Laboratory–developed series of scripts, written to dramatically simplify the computation of 

crystalline density and heat of formation, were used to evaluate the performance properties for the 3,7-diamino-2,4,6,8-

tetranitro-1,5-diazanaphthalene (DATNP) (1) and 3,7-diamino-2,4,6,8-tetranitro-1,5-diazanaphthalene 1,5-N-oxide 

(DATNPO) (2) notional energetic materials. Additionally, a qualitative estimation of the impact sensitivities has been 

calculated. This report outlines the procedures used to generate this information, as well as Cheetah calculations using the 

predicted crystalline density and heat of formation.

15. SUBJECT TERMS

computational toolbox, script, crystalline density, heat of formation, impact sensitivity, energetic materials

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Edward FC Byrd

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Unclassified

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410-306-0729 Standard Form 298 (Rev. 8/98)

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iii

Contents

List of Figures iv

List of Tables iv

Acknowledgments v

1. Introduction 1

2. Results and Discussion 1

3. Conclusions 4

4. References 5

List of Symbols, Abbreviations, and Acronyms 6

Distribution List 7
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iv

List of Figures

Fig. 1 Optimized structure of a) 1 and b) 2 ......................................................2

Fig. 2 Electrostatic potential map of 1, without a) and with b) molecule 

overlay....................................................................................................3

Fig. 3 Electrostatic potential map of 2, without a) and with b) molecule 

overlay....................................................................................................3

List of Tables

Table 1 Computed heats of formation and crystalline densities for 1 and 2.......2

Table 2 Cheetah predicted properties for 1 and 2 ...............................................3
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v

Acknowledgments

Dr Betsy Rice and Jennifer J Hare are acknowledged for their efforts in the original 

coding of the neutral heat of formation and EDAT tools, respectively. Dr Anthony 

Yau is acknowledged for his work in revising the EDAT code. Dr James Ianni

(Applications Engineer with Lockheed-Martin, contractor to the US Army 

Research Laboratory Department of Defense [DOD] Supercomputing Resource 

Center [ARL DSRC]) is acknowledged for his “gsubmit” script, initially written for 

the ARL DSRC. Dr Betsy Rice is acknowledged for running the Cheetah 

calculations. All computations were performed at the ARL DSRC, Aberdeen 

Proving Ground, MD. Calculations were performed at the behest of Dr Gary K 

Windler (Los Alamos National Laboratory).
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1

1. Introduction

US Army Research Laboratory (ARL) researchers have achieved robust theoretical 

models capable of predicting performance properties, such as heats of formation,

1,2

densities,3,4 and impact sensitivity5 of energetic materials, and have begun growing 

advanced synthesis capabilities to realize notional materials. This dual capability 

allows synthetic and formulation chemists to safely and quickly screen candidate 

materials to focus efforts only on the most promising compounds. For an in-depth 

explanation of the different theoretical methods employed herein, please refer to 

previous works.6,7 This technical note will detail theoretical predictions of heat of 

formation, density, sensitivity, and performance for the 3,7-diamino-2,4,6,8-

tetranitro-1,5-diazanaphthalene (DATNP) (1) and 3,7-diamino-2,4,6,8-tetranitro1,5-diazanaphthalene 1,5-N-oxide (DATNPO) (2).8

2. Results and Discussion

The properties of 1 and 2 (Figs. 1a–b) were predicted using the ARL-developed

scripts described in more detail in a previous report.

7 For the estimation of the 

impact sensitivities, the electrostatic maps on the 0.001 isosurfaces were generated 

with the scalar range of the electrostatic surface potential (ESP) ranging from –0.05 

to 0.075. Recall that for this visualization methodology, regions of large positive 

charge (i.e., electron deficient regions, labeled as red) over the backbone of the 

structure tend to indicate increased sensitivity.
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2

Fig. 1 Optimized structure of a) 1 and b) 2

The computed heats of formation and crystalline densities for these molecules are 

presented in Table 1.

Table 1 Computed heats of formation and crystalline densities for 1 and 2

Molecule

Solid phase heat of 

formation 

(kcal/mol)

Density 

(g/cm3

)

1 25.899 1.863

2 46.903 1.932

Additionally, we plot the ESP maps for 1 (Figs. 2a–b) and 2 (Figs. 3a–b) with and 

without the molecule overlaid on the ESP. When the images are analyzed, we would 

quantify both molecules as slightly sensitive to insensitive. We performed Cheetah 

8.0 calculations9 to predict the performance parameters using the predicted heats of 

formation and densities. At the Chapman-Jouguet point, Cheetah yields the values 

shown in Table 2. 
3

Fig. 2 Electrostatic potential map of 1, without a) and with b) molecule overlay

Fig. 3 Electrostatic potential map of 2, without a) and with b) molecule overlay

Table 2 Cheetah predicted properties for 1 and 2

Molecule Pressure 

(GPa)

Shock velocity 

(km/s)

Temperature

(K)

Total energy of 

detonation 

(TNT eqv. 

per cm3)

Total energy 

of detonation 

(TNT eqv. 

per g)

1 27.182 8.033 3204.0 1.175 1.043

2 32.745 8.643 3692.8 1.397 1.196

Note: TNT = trinitrotoluene
4

3. Conclusions

The ARL-developed software tools were used to predict the heats of formation and 

crystalline densities of the 3,7-diamino-2,4,6,8-tetranitro-1,5-diazanaphthalene 

(DATNP) (1) and 3,7-diamino-2,4,6,8-tetranitro-1,5-diazanaphthalene 1,5-Noxide (DATNPO) (2) molecules. Using this predicted data, we then ran Cheetah 

calculations to predict the performance of these materials. Additionally, we 

predicted the qualitative impact sensitivities of these compounds using electrostatic 

potential maps. This information has been transitioned back to the requesting 

synthetic chemist, Dr Gary K Windler of Los Alamos National Laboratory.
5

4. References

1. Byrd EFC, Rice BM. Improved prediction of heats of formation of energetic 

materials using quantum mechanical calculations. J Phys Chem A. 

2006;110(3):1005–1013; ibid 2009;113:5813. 

2. Byrd EFC, Rice BM. A comparison of methods to predict solid phase heats of 

formation of molecular energetic salts. J Phys Chem A. 2009;113(1):345–352.

3. Rice BM, Hare JJ, Byrd EFC. Accurate predictions of crystal densities using 

quantum mechanical molecular volumes. J Phys Chem A. 2007;111(42):

10874–10879.

4. Rice BM, Byrd EFC. Evaluation of electrostatic descriptors for predicting 

crystalline density. J Comp Chem. 2013;34(25):2146–2151.

5. Rice BM, Hare JJ. A quantum mechanical investigation of the relation between 

impact sensitivity and the charge distribution in energetic molecules. J Phys 

Chem A. 2002;106(9):1770–1783.

6. Byrd EFC. Theoretical prediction of the heat of formation, density and relative 

sensitivity for 3,7-dinitro-[1,2,4]triazolo[5,1-c][1,2,4]triazin-4-amine. 

Aberdeen Proving Ground (MD): Army Research Laboratory (US): 2015 Apr. 

Report No.: ARL-TN-0680.

7. Byrd EFC. On the failure of correlating partitioned electrostatic surface 

potentials using Bader’s atoms-in-molecules theory to impact sensitivities. 

Aberdeen Proving Ground (MD): Army Research Laboratory (US); 2013 Sep. 

Report No.: ARL-TR-6206.

8. Windler GK. Los Alamos National Laboratory, Los Alamos, NM. Private 

communications, 2015 Sep.

9. Bastea S, Fried LE, Glaeseman KR, Howard WM, Kuo IFW, Souers PC,

Vitello PA. Cheetah 8.0 thermochemical code. Livermore (CA): Energetic 

Materials Center, Lawrence Livermore National Laboratory; 2015.
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List of Symbols, Abbreviations, and Acronyms

ARL US Army Research Laboratory

cm3 grams per cubic centimeter

DATNP 3,7-diamino-2,4,6,8-tetranitro-1,5-diazanaphthalene

DATNPO 3,7-diamino-2,4,6,8-tetranitro-1,5-diazanaphthalene 1,5-N-oxide

DSRC Department of Defense (DOD) Supercomputing Resource Center

ESP electrostatic surface potential

kcal/mol kilocalories per mole (unit of energy)

TNT trinitrotoluene
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