ARL-TN-0748 ● APR 2016

US Army Research Laboratory

Theoretical Prediction of the Heats of 

Formation, Densities, and Relative Sensitivities 

for 2-(azidomethyl)-2-nitropropane-1,3-diyl 

dinitrate (AMDNNM), bis-aminofurazan 

diamino-octanitro-azobenzene (BAFDAONAB), 

and bis-nitrofurazan diamino-octanitroazobenzene (BNFDAONAB)

by Edward FC Byrd

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Destroy this report when it is no longer needed. Do not return it to the originator.
ARL-TN-0748 ● APR 2016

US Army Research Laboratory

Theoretical Prediction of the Heats of 

Formation, Densities, and Relative Sensitivities 

for 2-(azidomethyl)-2-nitropropane-1,3-diyl 

dinitrate (AMDNNM), bis-aminofurazan 

diamino-octanitro-azobenzene (BAFDAONAB), 

and bis-nitrofurazan diamino-octanitroazobenzene (BNFDAONAB)

by Edward FC Byrd

Weapons and Materials Research Directorate, ARL

Approved for public release; distribution is unlimited.

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

April 2016

2. REPORT TYPE

Technical Note

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1 November 2015–31 January 2016

4. TITLE AND SUBTITLE

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

Sensitivities for 2-(azidomethyl)-2-nitropropane-1,3-diyl dinitrate (AMDNNM), 

bis-aminofurazan diamino-octanitro-azobenzene (BAFDAONAB), and bisnitrofurazan diamino-octanitro-azobenzene (BNFDAONAB)

5a. CONTRACT NUMBER

5b. GRANT NUMBER

5c. PROGRAM ELEMENT NUMBER

6. AUTHOR(S)

Edward FC Byrd

5d. PROJECT 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-0748

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14. ABSTRACT

Using a series of scripts developed by the US Army Research Laboratory, written to dramatically simplify the computation of 

crystalline density and heat of formation, the performance properties were evaluated for the 2-(azidomethyl)-2-nitropropane1,3-diyl dinitrate (AMDNNM), bis-aminofurazan diamino-octanitro-azobenzene (BAFDAONAB), and bis-nitrofurazan 

diamino-octanitro-azobenzene (BNFDAONAB) notional energetic materials. A qualitative estimation of the impact 

sensitivities has also been calculated. This report outlines the procedures used to generate this information and includes

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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410-306-0729

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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. Conclusion 6

4. References 7

List of Symbols, Abbreviations, and Acronyms 8

Distribution List 9
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iv

List of Figures

Fig. 1 Optimized structure of a) AMDNNM , b) BAFDAONAB , and c) 

BNFDAONAB.......................................................................................2

Fig. 2 Electrostatic potential map of AMDNNM: a) without and b) with 

molecule overlay....................................................................................3

Fig. 3 Electrostatic potential map of BAFDAONAB: a) without and b) with 

molecule overlay....................................................................................4

Fig. 4 Electrostatic potential map of BNFDAONAB: a) without and b) with 

molecule overlay....................................................................................5

List of Tables

Table 1 Computed heats of formation and crystalline densities for AMDNNM, 

BAFDAONAB, and BNFDAONAB.....................................................3

Table 2 Cheetah-predicted properties for AMDNNM, BAFDAONAB, and 

BNFDAONAB.......................................................................................5
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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 Education Data Analysis Tool (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 

Supercomputing Resource Center [ARL DSRC]) is acknowledged for his 

“gsubmit” script, initially written for the ARL DSRC. All computations were 

performed at the ARL DSRC, Aberdeen Proving Ground, MD. Calculations were 

performed at the behest of Dr David Boruta (Naval Surface Warfare Center–Indian 

Head, MD).
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vi

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1

1. Introduction

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

models capable of predicting performance properties including 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

2-(azidomethyl)-2-nitropropane-1,3-diyl dinitrate (AMDNNM), bis-aminofurazan 

diamino-octanitro-azobenzene (BAFDAONAB), and bis-nitrofurazan diaminooctanitro-azobenzene (BNFDAONAB) notional energetic materials.

8

2. Results and Discussion

The properties of AMDNNM, BAFDAONAB, and BNFDAONAB (Figs. 1a–1c) 

were predicted using ARL tools.7 To estimate 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. For this 

visualization methodology, regions of large positive charge (i.e., electron-deficient 

regions, labeled in red) over the backbone of the structure tend to indicate increased 

sensitivity.
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2

Fig. 1 Optimized structure of a) AMDNNM , b) BAFDAONAB , and c) BNFDAONAB
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3

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 AMDNNM, 

BAFDAONAB, and BNFDAONAB

Molecule

Solid phase heat of 

formation 

(kcal/mol)

Density 

(g/cm3

)

AMDNNM 1.182 1.720

BAFDAONAB 175.518 1.898

BNFDAONAB 180.912 1.934

Additionally, we plot the ESP maps for AMDNNM (Figs. 2a and 2b), 

BAFDAONAB (Figs. 3a and 3b), and BNFDAONAB (Figs. 4a and 4b) with and 

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

quantify AMDNNM as moderately sensitive, BAFDAONAB as slightly sensitive 

to insensitive, and BNFDAONAB as sensitive. That said, chemist intuition would 

classify AMDNNM as likely to be very sensitive. It would be of interest to compare 

the experimental with the predicted results for AMDNNM. 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.

Fig. 2 Electrostatic potential map of AMDNNM: a) without and b) with molecule overlay
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4

Fig. 3 Electrostatic potential map of BAFDAONAB: a) without and b) with molecule 

overlay
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5

Fig. 4 Electrostatic potential map of BNFDAONAB: a) without and b) with molecule 

overlay

Table 2 Cheetah-predicted properties for AMDNNM, BAFDAONAB, and BNFDAONAB

Molecule Pressure 

(GPa)

Shock velocity 

(km/s)

Temperature 

(K)

Total 

energy of 

detonation 

(TNT 

equivalent)

(per cm3)

Total 

energy of 

detonation 

(TNT 

equivalent)

(per g)

AMDNNM 29.348 8.275 3,663.1 1.349 1.297

BAFDAONAB 31.278 8.545 3,665.6 1.339 1.167

BNFDAONAB 35.442 9.011 4,116.3 1.435 1.227

Note: TNT = trinitrotoluene.
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3. Conclusion

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

crystalline densities of the AMDNNM, BAFDAONAB, and BNFDAONAB 

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 

David Boruta of Naval Surface Warfare Center–Indian Head.
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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.

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. Boruta DT. Naval Surface Warfare Center, Indian Head, MD. Private 

communications, 2015 Nov and 2016 Jan.

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

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

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

AMDNNM 2-(azidomethyl)-2-nitropropane-1,3-diyl dinitrate

ARL US Army Research Laboratory

BAFDAONAB bis-aminofurazan diamino-octanitro-azobenzene

BNFDAONAB bis-nitrofurazan diamino-octanitro-azobenzene

ESP electrostatic surface potential

TNT trinitrotoluene
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