Combustion, Explosion, and Shock Waves, Vol. 41, No. 3, pp.

264277, 2005

Novel Ultrahigh-Energy Materials

M. B. Talawar,1 R. Sivabalan,1 S. N. Asthana,1 and H. Singh1
UDC 536.46

Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 3, pp. 2945, MayJune, 2005. Original article submitted April 8, 2004.

This paper reviews the recent work carried out in the eld of modern high-energy materials (HEMs) with the emphasis on homoleptic polynitrogen compounds. A large volume of quantum-chemical investigations have predicted the possibility of existence of polynitrogen compounds not only as short-lived transient species but also in the form of isolable discrete molecules. Despite the theoretical speculations, only a few polynitrogen ions are known today in addition to well-entrenched N1 discovered 3 almost 100 year ago. Extraordinary potential of these green molecules to deliver high amounts of energy in comparison with todays and tomorrows most powerful HEMs, namely, hexanitrohexaazaisowurtzitane (CL-20) and octanitrocubane (ONC), has fuelled the imagination of propellant and explosive engineers and technologists. Research activities are in progress in many quantum-chemical schools to explore the possibility of other promising polynitrogen compounds. After the recent discovery of key synthons/building blocks Mg(N5 )2 , N1+ SbF1 , N1+ SbF11 , N1+ , N1+ SnF6 , and 5 6 5 5 5 N1+ Sn(CF3 )4 , the wealth of polynitrogen compounds is just waiting to be harvested 5 by the HEMs community. There are ambitious plans all over the globe to realize N60 , which only prove a eco-friendly dense powerhouse of energy. Key words: polynitrogen, high-energy materials.

INTRODUCTION With the increasing importance of satellites for communication and exploration of space as well as ambitious space-shuttle programs, the sphere of applications of propellants has extended tremendously from the defense to the space sector. Explosives are also nding applications in specic areas like metal cladding, mining, and demolition of dilapidated structures. Applications of propellants and explosives as clean sources of power generation are also being envisaged. A quantum jump in the usage of propellants has brought into focus the issue of environment-friendly systems. The challenge of increasing lethality of warheads has evinced interest in High-Energy Dense Materials (HEDMs). Mammoth projects undertaken all over the globe have brought into foray a totally new spectrum of HEMs during the last two decades. Therefore, a new era of HEMs has dawned on the sector of propellants, explosives, and
1

pyrotechnics. The revolution in synthesis and manufacturing technologies has opened the possibilities of realizing HEDMs that were considered a theoretical curiosity a few years ago.

GLOBAL SCENARIO Composite ammonium perchlorate (AP)-based and composite modied double-base (CMDB) propellants may be dislodged from the premier position today with the emergence of eco-friendly oxidizers: ammonium dinitramide (ADN) [1, 2] and hydrazinium nitroformate (HNF) [3, 4]. Their heat of formation (151 and 71 kJ/mole, respectively) is higher than that of AP; therefore, these materials are capable of oering propellants with the performance level exceeding 260 sec despite their lower oxygen balance. Moreover, in contrast to nitramines, they undergo highly exothermic combustion reactions near the surface, leading to ecient heat feedback to the deagrating surface, enhancing

High Energy Materials Research Laboratory, Pune-411021, India; mbtalawar@yahoo.com.

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0010-5082/05/4103-0264 c 2005 Springer Science + Business Media, Inc.

Novel Ultrahigh-Energy Materials

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TABLE 1
Modern High-Energy Materials

266 the burning rates. ADN was synthesized at the Zelinsky Institute of Organic Chemistry (ZIOC, Moscow, Russia) during 1970s, and subsequently ADN propellants were productionized in Russia. The work on HNF was carried out mainly at the Prins Maurits Laboratory (the Netherlands). Today, it is manufactured by Aerospace Propulsion Products (APP, the Netherlands) at the scale of 300 kg/year (Table 1). Azide polymers, particularly, glycidyl azide polymer (GAP) [5, 6], and co-polymers of bisazido methyloxetane (BAMO) [7], have entered the domain of advanced propulsion systems. Replacement of current workhorse binder [hydroxyl-terminated polybutadiene (HTPB)] by these energetic materials will act as a force multiplier. Poly-3-nitratomethyl3-methyloxetane (PNMMO) [8] and poly-glycidyl nitrate (PGN) [9] have also made foray in the area of advanced systems. However, their stability problems need to be tackled. The BAMO and nitratomethyl methyloxetane (NMMO) co-polymer is fast emerging as an energetic thermoplastic elastomer [7,10] having wide applications in the area of extruded composite rocket propellants as well as pressed/sheet explosives. Bis(2,2-dinitropropyl)formal/acetal (BDNPF/A) [11, 12] and metriol trinitrate (TMETN) [13] have also gained prominence as potential energetic plasticizers for rocket propellants. The structures of modern high-energy materials are presented in Table 1. EMERGING TRENDS Polycyclic compounds containing interconnected, closely packed atoms referred to as cage compounds are of great interest to HEM technologists. Conversion of polycyclic materials to nitro/nitrato/nitramino derivatives results in realization of high-power packed storehouses of energy. However, straightforward nitration of precursor caged hydrocarbons is not viable. It results in formation of byproducts and often cleavage of the carefully constructed cage structure. Such complexities led to a strong opinion that cage compounds, such as hexanitrohexaazaisowurtzitane (CL-20), will remain at the most a laboratory curiosity. However, innovative nitration approaches and selection of highly specialized nitrating agents as well as reaction conditions made it possible to realize CL-20 at the pilot scale after lab-scale synthesis reported by Nielsen [14] during late 1990s. CL-20 can outstrip tetranitro tetramethylene cyclooctane (HMX) in terms of velocity of detonation (VOD). It is expected to give 14% higher energy than HMX. The technological breakthrough [15] in this direction gave an impetus to research in the area of another fascinating HEM, octanitrocubane (ONC).

Talawar, Sivabalan, Asthana, and Singh In the early 1980s, ONC was projected as a highpotential energetic material [16, 17]. Statistical and computational approaches predicted a density of 2.1 to 2.2 g/cm3 of ONC having a perfect oxygen balance. Recently published reports [18] estimate its heat of formation to be 594 kJ/mole, which is higher than the heat of formation of hexanitrobenzene (HNB, 200 kJ/mole). The energy content of HNB is lowered by the stabilizing resonance energy of the aromatic system, whereas the energy content in ONC is augmented due to the strain energy of the cubane. The theoretically computed VOD of ONC is 10 km/sec. As a matter of fact, synthesis of cubane and bishomocubane was reported [19] way back in 1966. The challenging task of nitration of cubanes to nitrocubanes was undertaken, and several discoveries were made, leading to the opening of new vistas of chemistry. The innovative photochemical method developed by Basher-Hashmi et al. [20, 21] was adopted to obtain cubane-2,4,6,8-tetracarboxy acid chloride. The wellknown Curtius rearrangement was employed to convert the latter to its isocyanate, which, on oxidation by dimethyl dioxerane, yielded 2,4,6,8-tetranitrocubane (TNC). The highly acidic nature of atomic hydrogen present in the TNC was expected to facilitate the synthesis of higher nitrocubanes (Scheme 1). Thus, straightforward nitration of TNC with nitrating agents such as N2 O4 , NO2 BF4 , and N2 O5 yielded complex mixtures. A novel approach [22] called interfacial nitration led to the long-awaited breakthrough. It involved freezing of a solution of an anion salt of TNC on a glass substrate and deposition of solid N2 O4 onto its surface. The reactants came into productive combination, and the glass was allowed to melt. In the method applied in [23], TNC was treated with 1.5 equivalents of NaN(TMS)2 at 78 C in a 1/1 tetrahydrofuran/-metyl tetrahydrofuran mixture, resulting in formation of the TNC monoanion. The solution was cooled to a temperature between 125 and 130 C. N2 O4 in cold isopentane was added to the highly viscous liquid, followed by nitric acid in cold diethyl ether, yielding pentanitrocubane (PNC). An increase in the NaN(TMS)2 proportion yielded hexanitrocubane (HNC), and subsequently heptanitrocubane (HpNC). But a further increase in the content of NaN(TMS)2 did not yield ONC, and it remained elusive for a long time, probably due to the high stability of the HpNC anion (Scheme 2). Zhang et al. [23] utilized more powerful oxidants, such as nitrosyl chloride, considering the high acidity of HpNC. Addition of an excess of NOCl to a solution of the lithium salt of HpNC in dichloromethane at 78 C followed by ozonisation at 78 C led to the synthesis

Novel Ultrahigh-Energy Materials

267

Scheme 1.

Scheme 2.

of ONC (the most eective modern energetic material) with a yield of 4555%. Thus, ONC acquired the status of the only nitrocubane synthesized in the last 18 years (Scheme 3). ONC is a stable white solid soluble in hexane and polar organic solvents. It sublimes without decomposition at atmospheric pressure at 200 C, and its samples have survived unchanged for 14 months in sealed glass tubes. The density of one polymorph of synthesized ONC is 1.979 g/cm3 , which is still lower than the calculated value, and attempts are continued to obtain a denser material.

Currently, ONC is quite expensive to synthesize owing to involvement of a large number of synthesis steps. The research is focused on economizing its synthesis. One of the projected inexpensive methods of ONC synthesis is tetramerization of dinitroacetylene (Scheme 4). The state-of-the art theoretical calculations [24] indicated that the free-energy change in dinitro-acetylene to octanitrocubane conversion is thermodynamically downhill by 417 kJ/mole, i.e., this reaction is thermodynamically feasible.

268

Talawar, Sivabalan, Asthana, and Singh

Scheme 3.

Scheme 4.

1,2,5-oxadiazoles (furazans) [25] and their 2-oxides [26] are also highly-promising building blocks for creation of high-performance materials owing to the high density of their molecular crystals and positive enthalpy of formation because of active oxygen atoms simultaneously present inside the molecular ring. Introduction of explosophoric groups to furazan and furoxan rings allows higher density and energetics. One interesting furoxan-based high-energy material obtained at ZIOC is 4,4-dinitro-3,3-diazenofuroxan (DNAF) [26]. The velocity of detonation in DNAF determined experimentally by extrapolation of data on pressed samples (85, 94, and 97% of the theoretical value) was reported to be 10 km/sec for a single-crystal density of 2.00 g/cm3 , which is close to ONC density. DNAF was successfully synthesized in three steps from a key synthon 3-azidocarbonyl-4-aminofuroxan (AzCAF). However, DNAF worthiness in comparison to CL-20 and ONC need to be proved in view of its low decomposition temperature (127128 C) and particularly high impact sensitivity. High-nitrogen-content high-energy materials (HNC-HEMs) [2729] are becoming the focal point of research in the area of advanced HEMs aimed at futuristic defence- and space-sector needs. The high energy content of HEMs stems from the presence of adjacent nitrogen atoms poised to form molecular nitrogen (N N). Such transformations are accompanied by enormous energy release due to the large dierence in the average energies of single N N (160 kJ/mole) and double N N (418 kJ/mole) bonds, compared to the mean energy of the triple bond N N (954 kJ/mole). As a natural consequence of their chemical structure, HNC-HEMs also generate a large volume of the gas (N2 ) per gram of HEM, projecting them as a possible material for clean gas generators.

The research in this direction commenced with the studies on relatively easily isolable materials from the class of azotetrazolates and tetrazines. The high potential of nitrogen-rich compounds, such as diamino azobis tetrazine (DAAT) [30, 31], dihydrazine tetrazine (DHTz) [31, 32], and some azotetrazolate salts [3335] was reported. DAAT having a high positive heat of formation (1032 kJ/mole) is considered as a potential HEM to be used in rocket propellants and insensitive high-explosive (IHE) formulations. Among tetrazolates, the triaminoguanidinium salt with the heat of formation equal to 560 kJ/mole and reasonable sensitivity characteristics competes with DAAT. DHTz may nd application as an eco-friendly pyrotechnic ingredient (see Table 1).

NOVEL ENERGETIC MATERIALS

Homoleptic polynitrogen compounds are the real contenders [36, 37] as HEMs of this class. Storage of the maximum amount of energy in a polynitrogen molecule would mean having the largest number of single N N bonds in its molecular structure. To obtain isolable and manageable homoleptic polynitrogens, the compound needs to possess a suciently high energy barrier to decomposition. Researchers at U.S. Air Force Oce of Scientic Research (AFOSR) have explored unusual polynitrogen molecules with the aim of nding new rocket fuels, which could surpass cryogenic systems based on hydrogen and liquid oxygen. Quantummechanical calculations suggest that N4 , N5 , N8 , and N10 are viable molecules.

Novel Ultrahigh-Energy Materials

269

Scheme 5.

N4 and N5 Compounds The WoodwardHoman rules have been applied to calculate the energy barrier of tetrahedral N4 to dissociate into two N2 molecules [38, 39]. It requires that two electrons from the highest occupied molecular orbital (HOMO) need to be promoted into the lowest unoccupied molecular orbital (LUMO). Theoretical calculations demonstrate that the energy barrier for such transitions is around 3050 kcal/mole for the N4 molecule, which is higher than that for trinitrotoluene (TNT), suggesting the possibility of the N4 molecule to exist. However, it is an oversimplication to consider single-step dissociation of the N4 molecule. In reality, several steps are expected to be involved in N4 dissociation, and a number of geometric congurations other than tetrahedral symmetry are likely to exist for the N4 molecule. Most of these congurations are transition states. It is conceptualized that the building principle and unique resonance stabilization of the well-known and exceptionally stable azide anion, where each N N bond has a full double-bond character, may be extended by adding N1+ containing four valence electrons to construct the N4 molecule and the N1+ ion (see Scheme 5). 5 Several quantum-chemical calculations have indicated that the tetrahedral form of N4 should be both stable and quite energetic. The production and identication of the N4 molecule, however, have not yet been conclusively demonstrated. Although N4 (II) and N1+ (III) are conceptual5 ized to contain (like azide ions) only cumulated linear N N bonds, the neighboring positive charges present in their structure, in contrast to N1 (I), render both 3 N4 and N1+ energetically unfavorable. Ab initio self5 consistent-eld (SCF), coupled-cluster, and many-body perturbation theory (MBPT) calculations also predict that tetrahedral N4 is metastable [40]. Quantum-mechanical calculations of the N1+ and 5 1 N5 isomers within the framework of the MollerPlesset perturbation theory (FU)/6-31G(d) [41] suggest that the most stable open-chain structure of N1+ has the C2v 5 symmetry. The natural bond orbital (NBO) analysis suggests that the stability of this cation is enhanced by hyperconjugation (see IV in Scheme 5). The limitations

of the neighboring positive charges can be remedied for N1+ by considering resonance structures (with the C2v 5 symmetry) with a bond order of 1.5 for the central N N bonds. The decomposition mechanism of pentanitrogen (N5 , N1 , and N1+ ), its clusters and ions was stud5 5 ied in [42] using ab initio molecular orbital (MO) calculations up to the Coupled Clusters Single Double and non-iterative Triple method [CCSD(T)] level with 6-31 + G(3dp) and aug-cc-pVTZ basis sets, as well as the Density Functional Theory (DFT)/Beckes gradient corrected exchange correlation density functions (B3LYP). These ndings suggest that the cyclic anion N1 and the open-chain cation N1+ may be relatively 5 5 stable with respect to N2 elimination, while the neutral N5 radical does not exist at all as a discrete species. A tremendous thrust to research in the area of polynitrogen compounds has been provided by the technological breakthrough achieved at the Air Force Research Laboratory (AFRL) on realizing the N1+ 5 molecule. An important discovery was the synthesis of the N1+ cation by the reaction of N2 F and AsF1 5 6 with HN3 in an anhydrous solution [43]. N1+ AsF1 is 5 6 a highly energetic white solid with a strong oxidizing nature: N2 F + AsF6 + HN3 N+ AsF + HF 5 6
78 C HF HF

HN3 + HF + AsF5 H2 N+ AsF 3 6 4N+ AsF + 2H2 O 4HF + 4AsF5 + 10N2 + O2 5 6 N+ AsF + NaN3 Na+ AsF + N+ N 5 6 6 5 3
Scheme 6.

It detonates violently with a detonation pressure four times that of HMX, and its specic impulse (Isp ) is twice as high as the value of Isp of todays monopropellants. Christe et al. [43] have also succeeded in preparing the N1+ SbF1 salt with high purity and 5 6 yield. This salt is surprisingly stable up to 70 C and exhibits low impact sensitivity, in contrast to N1+ AsF1 , which is reported marginally stable at 5 6 room temperature. Attempts to recrystallize the compound from the SO2 /SO2 ClF solution yielded another new N5 F salt, namely, N1+ Sb2 F1 . The crystallo5 11 graphic studies conrmed the V-shaped conguration

270 of these compounds. The bond lengths and bond angles for N1+ [N1 N2 N3 N2 N1] calculated at the 5 B3LYP level of theory are r1 (N1 N2) = 1.11 and A r2 (N2 N3) = 1.31 with dihedral angles 166.6 A (N1 N2 N3) and 110.3 (N2 N3 N2). Eorts are in progress in many schools to convert N1+ AsF1 to its 5 6 N8 adduct. The discovery of N1+ has been widely acclaimed 5 internationally as the third all-nitrogen species to be isolated in the discrete form and the rst in over 100 years. Exchange reactions (Scheme 7) were used to convert N1+ SbF1 into N1+ [B(CF3 )4 ]1 and (N5 )1+ SnF1 5 6 5 2 6 [44]. The latter salt is noteworthy because it contains two N1+ ions per anion, thus demonstrating that salts 5 with contacting polynitrogen cations could be prepared. This constitutes an important milestone toward the ultimate goal of synthesizing a stable ionic nitrogen atmosphere. Stepwise decomposition of (N5 )2 SnF6 yielded N5 SnF5 . Attempts to isolate FN5 from (N5 )2 SnF6 thermolysis were unsuccessful, yielding only the expected decomposition products, FN3 , trans-N2 F2 , NF3 , and N2 : N2 FMF6 + HN3 N5 MF6 + HF, N5 SbF6 + MY N5 Y + MSbF6 , 2N5 SbF6 + Cs2 SnF6 (N5 )SnF6 + 2CsSbF6 ,
78 C HF HF

Talawar, Sivabalan, Asthana, and Singh a structure does not correspond to a minimum on the potential energy surface. To increase the stability of N6 without compromising the energy-storage ability, it is envisaged to introduce other hetero-atoms into the structure. Thus, repulsion between electron pairs of adjacent nitrogen atoms can be overcome by introducing oxygen at the 1,3,5-positions of N6 resulting in formation of N O co-ordinate bonds. The calculations of [4547] suggest reasonable stability of N6 with an activation energy barrier of 40 kcal/mole.

N8 : The Most Widely Studied Potential Polynitrogen Compound of HEM Importance Scientists are currently focusing their investigations on developing a reaction system to combine N1+ 5 with N1 in an attempt to isolate a neutral N8 com3 pound in the form of a ionic salt N1+ N1 or covalently 5 3 bonded azidopentazole. If such compounds could be realized in a stable form, they could be monopropellants with over 200% greater energy than hydrazine widely used in upper-stage and spacecraft propulsion. Nguyen and Ha [48] carried out ab initio MO calculations at the quadratic CI [QCISD(T)/6-31G(d)], CCSD(T), and Double-z plus Polarization (DZP) levels based on MP2/6-31G(d) optimized geometries. These calculations show that the azidopentazole structure is likely to be the global minimum of the N8 isomers, lying 13 and 18 kcal/mole below the acyclic diazidyldiimide and cyclic pentazole (ve-member ring consisting of nitrogen atoms) analog, respectively. Azidopentazole is characterized by a signicant energy barrier to ring closure and is expected to be stable with respect to cycloreversion. Leininger et al. [49] have also applied ab initio molecular electronic structure methods to examine three isomers of N8 : octaazacubane, cyclooctatetraene with D2d symmetry, and a pentazole analog with a planar bicyclic form. Using a DZP basis set, geometries were optimized with the HartreeFock self-consistent-eld (HF-SCF) method and second-order MP2 as well as congurationinteraction (CISD) and coupled-cluster (CCSD) methods. Vibrational frequencies and IR intensities have been obtained at the SCF and MP2 levels of theory. Although cubane (C8 H8 ) and cyclooctatetraene (C8 H8 ) are known experimentally, unsubstituted penatazole has never been synthesized; nevertheless, the vibrational analysis indicates that all three nitrogen analogs, including the pentazole analog, represent potential energy minimums. Metastability is attributed to two additional p-electrons present in the rst two com-

(N5 )2 SnF6 N5 SnF5 + FN5 , N5 SnF5 SnF4 + FN5 ,

2 N5 SbF6 + K[B(CF3 )4 ] N5 [B(CF3 )4 ]

SO

64 C

+KSbF6

(M = Sb, As)

Scheme 7.

The presence of the delocalized electronic structure of N1 seems to oer stronger N N bonds. As a mat5 ter of fact, N1 should have been the building block 5 for polynitrogen molecules from an electronic-structure viewpoint. However, its extreme sensitivity combined with the fact that it cannot be stabilized in a structure without a large delocalized aromatic ring has made its use dicult.

N6 Compound The N6 molecule appears to be another interesting system with an apparent benzene-type structure. However, high-precision theoretical investigations at the Quadratic Conguration Interaction including Single and Double substituents (QCISD) level reveal that such

Novel Ultrahigh-Energy Materials pounds but not in pentazole. Further, since all three minimums lie very high with respect to the energy of four N2 molecules, their potential application as highenergy-density materials (HEDMs) have been reported. Calculations on the stability of N8 [50] indicate that, if it could be synthesized, its dissociation into four N2 molecules might result in energy release estimated as (530 50) kcal/mole. The potential energy surfaces for the synthesis and decomposition reactions of N8 (CS ) N+ + N and the isomerization reaction 5 3 of N8 (CS ) to N8 (C2h ) were investigated in [51] by DFT. The barrier heights of N8 (CS ) N+ + N in the for5 3 ward and reverse directions were predicted to be 23.4 and 2.0 kcal/mole, respectively. The barrier height for the isomerization reaction of N8 (CS ) to N8 (C2h ) was predicted to be 4.0 kcal/mole at the QCISD/6-311 + G and B3LYP/6-311 + G levels. Fau and Bartlett [46] also reported transitional states for various interconversions and dissociative reactions to assess the stability of N+ and N . Seven structures appear to be at the 5 3 energy minimums at the B3LYP/aug-cc-pVDZ (augmented double polarized valence) and MBPT(2)/augcc-pVDZ levels of theory, i.e., ve diazidyldiazenes and two diazidylaminonitrenes or N3 N5 complexes. Gibbs free energies based on CCSD(T)/aug-cc-pVDZ singlepoint calculations strongly suggest that only four of the diazidyldiazene structures have minimums at higher levels of theory. In diazidyldiazenes, the loss of N2 from one of the azidyl end groups is as likely as the loss of both azidyl groups. Thus, isolation of covalently bonded N8 from N+ and N will be dicult because the most 5 3 probable product has a decomposition barrier of only 18 kcal/mole. Mutual neutralization is likely to follow fragmentation. A theoretical study was presented by Gagliardi et al. [52] on dissociation of N8 octaazapentalene (I) to four N2 molecules with the use of the MultiCongurational Self-Consistent Field (MC-SCF) and MP2 methods. The reaction proceeds via isomerization of (I) to azidopentazole (II), which then dissociates directly into four N2 molecules. The calculations determined the relative energies of congurations I and II, as well as two transitional states involved into the dissociation reaction, and indicate that conguration II was 13 kcal/mole more stable than conguration I. The barrier to dissociation of N8 into four N2 molecules was computed as 19 kcal/mole. An ab initio study of fully optimized structures of thirteen N8 isomers at the HF/6-31G(d) and MP2/6-31G levels was reported in [53]. These isomers are nitrogen analogs of various hydrocarbon skeletons: 1,2dihydropentalene, cyclooctatetraene (tub form), barrelene bicyclo[2,2,2]octa-2,5,7-triene, bicyclo[4,2,0]octa-

271

TABLE 2
Homoleptic Polynitrogen Molecules to be Synthesized Yet

2,4,7-triene (C2 and C2v ), tricyclo[3,3,0,02.6 ]octa-3,7diene, tetracyclo[4,2,0,02.4 ,03.5 ]octa-7-ene, anti-tricyclo[4,2,0,02.5 ]octa-2,6-diene, syn-tricyclo [4,2,0,02.5 ]octa2,6-diene, cuneane, octabisvalene, cyclooctatetraene (crown form), and cubane. Twelve local minimums were found on the potential energy hypersurface at the HF/6-31(d) basis set via vibrational frequency calculations at the same levels of theory. The eect of elec-

272 tron correlation on various stationary point structures was examined using MP2/6-31G(d) calculations. Only eleven N8 isomers appear to be stable (with the exceptions of barrelene bicyclo[2,2,2]octa-2,5,7-triene and cyclooctatetraene (crown form)). Dissociation of this isomer into four N2 molecules is predicted by the MP2/631G(d) model to result in energy release of the order of 247478 kcal/mole (including zero-point energy correction). The lowest vibrational frequency predicted by both MP2/6-31G(d) and HF/6-31G(d) models suggests that N8 -cubane has the highest energetic rigidity among these isomers and is a stable molecule. In addition to the octaazacubane structure (Qh symmetry, 1), Tian et al. [54] investigated two new structures without N N double bonds with D2h (2) and C2v (3) symmetries, respectively. The C2v structure may be designated for octaazacubane. The single-point energies were also estimated for octaazacubane at the CISD+Q/DZP level of theory with CISD/DZP geometries and at the CCSD(T)/DZP level with CCSD/DZP geometries. Vibrational frequencies and their IR intensities were obtained for N8 by the SCF, MP2, and DFT methods. The calculation results show that both new isomers correspond to minimums on the N8 potential energy hypersurface and have higher energies than isomers containing N N double bonds. Evangelisti and Gagliardi [55] described Complete Active Space SelfConsistent Field (CAS-SCF) calculations for cubic N8 and studied decomposition of N8 (N8 4N2 ) in D4h symmetry. Calculations with three basis sets revealed the N8 energy release to be 526 kcal/mole and the activation barrier to dissociation to be 159 kcal/mole. Gagliardi et al. [56] reported isomerization of cubic N8 to a planar bicyclic structure analogous to pentazole by using the MC-SCF and second-order Complete Active-Space Perturbation Theory (CASPT2). Five local minimums on the potential energy surface were found, and the energies of transitional states between each two consecutive minimums were determined. The calculation results show that all steps in the isomerization process, except one, can proceed via a set of transitional states with moderately high energy barriers (1020 kcal/mole). The highest-quality results obtained by Leininger et al. [49] place the pentazole-like structure approximately at 225 kcal/mole above four N2 molecules, 198 kcal/mole below octaazacubane, and 35 kcal/mole below the D2d structure. Ab initio and DFT calculations suggest that Nn molecules based on pentazole units will meet the aromaticity criteria, like furan and pyrrole. The cyclopentadienyl anion, such as octaazapentalene (with 10 -electrons), is also expected to be aromatic in nature and, thus, highly stable.

Talawar, Sivabalan, Asthana, and Singh

TABLE 3
Synthesized and Characterized Homoleptic Polynitrogen Molecules

N10 Compound It is speculated that the short-lived N1 ion can 5 be trapped by interacting with the N1+ cation to real5 ize the N10 molecule. Manaa [57] claims that bridging of the N N bond in N10 may be remarkably strong, considering the energy barrier of 93 kcal/mole for N10 cleavage into two N5 moieties. It will also permit a facile rotation of one ring with respect to the other ring to acquire a stable conguration. Formation of N10 from N1+ 5 and N1 was also considered with the use of the MP2 5 and DFT-B3LYP methods. On the basis of quantumchemical calculations, Manaa showed [57] that N10 , or dipentazole, if it could be synthesized, would contain a mixture of single and double bonds and would be metastable. Each of its two pentazole ions (N1+ and 5 N1 ) would be at and connected perpendicularly to 5 the other. The bridging bond between the ions is predicted to be strong and yet exible enough to allow the relative motion. Ab initio and DFT calculations also suggest that D2d -symmetry bispentazole is at the lowest energy N10 minimum but is 260 kcal/mole higher in energy than ve N2 molecules. For strain-free molecules, the average deviation is 2.6 kcal/mole between the DFT energies and those based on the increment scheme. The synthesis of N5 and N10 molecules has been claimed by Matsunaga et al. [58].

Novel Ultrahigh-Energy Materials

273

TABLE 4
Key Synthons Proposed for the Synthesis of Futuristic Unknown Polynitrogen Compounds

N12 , N14 , N16 , N18 , and N20 : Potential Higher Analogs of Polynitrogen-Based High-Energy Materials

Klapotke and Harcourt [59] carried out ab initio HF/6-31 G(d) molecular orbital calculations for Nn components (n = 12, 10, and 8) and suggested a qualitative valence bond (VB) mechanism for interconversion N12 N10 + N2 and N10 N8 + N2 . Sun and Chen [53] studied the bond energy of small- and medium-size nitrogen clusters (N8 , N10 , N12 , N14 , N16 , N20 , and N24 ) at dierent levels of quantum-chemical investigations. All these methods show that the energies of N N bonds in polynitrogen clusters are higher than the standard energy of the N N single bond but lower than the

standard energy of the N N double bond. From the viewpoint of the total bond energy, the N20 compound appears to be the most stable one among these clusters. The cage-like structure of the N18 molecule with C2v symmetry was optimized at the Restricted Hartree Fock (RHF/4-31G ), RHF/6-31G , DFT(B3LYP, B3P86, BHLYP)/6-31G , and MP2(full)/6-31G levels of theory. Harmonic vibration frequencies and their IR and Raman intensities were also reported at the RHF/431G , RHF/6-31G , and B3P86/6-31G levels. The examined cage-like structure corresponds to a local minimum on the potential energy hypersurface, and its stability is commensurable with the stability of the dodecahedral N20 molecule. The calculations show that the energy of the N18 conguration with C2v symmetry is

274

Talawar, Sivabalan, Asthana, and Singh

TABLE 5
Other Stabilized Polynitrogen Molecules with a High Nitrogen Content

Scheme 8.

both methods were close to each other. Possible values of the enthalpy of formation Ha and Gibbs energy Ga for the atomization reaction prove that N20 is stable.

N60 : Futuristic Celebrity of HEMs Community as an Ultrapowerful HEM The C60 molecule (fullerene) exists, why not N60 ? N10 is currently projected as a key polynitrogen that can serve as a building block for clustering into a nitrogen analog of buckminster fullerene comprising 32 to 600 carbon atoms. Because nitrogen atoms are normally triple-bonded, no one had previously examined the possibility of creating a nitrogen fullerene, which appears to be an oddity. According to Manaa [57], it might be possible to join six N10 molecules into a soccer-ball-shaped 60-atoms molecule, on the lines of carbon-based buckminster fullerene, by subjecting N10 to ultrahigh pressures. The synthesis of N60 proposed by Manaa [57] is presented in Scheme 8. Huge amounts of energy are bound to be released on cleavage of tight bonds of the N60 molecule. Three absorption bands in the IR spectrum of the N60 molecule are predicted at 608 (56), 701 (94), and 1153 (4) cm1 . Engelke and Stine [50] estimated the density of N60 between 2.25 and 2.67 g/cm3 , and the predicted enthalpy of formation (Hf ) is approximately 546 kcal/mole. The predicted energy release due to N60 decomposition into 30 molecules of N2 is 2400 kcal/mole. The ChapmanJouguet (CJ) performance with nitrogen considered as the basic decomposition product was calculated by applying the Becker KistiakowskyWilsion (BKW) and Eective Spherical Potential (ESP) equations of state for N60 and suggest its high potential as a high-energy material. The ball-and-stick models of potential polynitrogen compounds [drawn by the software named Advanced

50 kcal/mole higher than that of nine N2 molecules. The resultant structure also suggests aromaticity of conjugated pentagons, which can stabilize cage-like polynitrogen clusters. Both the ab initio (STO-3G) and modied semi-empirical (INDO) methods were applied to molecular orbital calculations of the N20 molecule. The stability of the examined cage-like structure turned out to be commensurable with the stability of the dodecahedral N20 molecule. The optimized bond distances between the nearest nitrogen atoms (N N) and most of the calculated thermodynamic data approximated by

Novel Ultrahigh-Energy Materials TABLE 6

Performance Parameters of Polynitrogen Compounds in Comparison to Conventional HEMs Density, g/cm3 1.9 2.00 1.91 2.1 1.752 1.85 1.974 2.151 2.211 2.283 2.67 Heat of Velocity of formation, detonation, kcal/mole HMX CL-20 DNAF ONC N4 N1+ 5 N6 N8 N10 N12 N60 C4 H8 N8 O8 C6 H6 N12 O12 C4 N8 O8 C8 N8 O16 N4 N5 N6 N8 N10 N12 N60 28.0 109.8 159.1 111.0 268.7 350 345.58 406.69 473.42 579.82 546 km/sec 9.1 9.4 10.0 10.1 13.24 12.51 14.04 14.86 12.08 12.53 17.31 Pressure of detonation, GPa 39.0 42.0 50.0 50.0 77.02 73.95 93.32 108.39 58.05 64.07 196.0

275

Substance

Formula

Chemistry Development (ACD) Chem sketch 133; www.acdlabs.com] are presented in Tables 25. The theoretically computed [5060] performance of polynitrogen compounds in comparison to conventional HEMs is presented in Table 6.

CONCLUSIONS Despite the extensive theoretical investigations indicating that polynitrogen molecules are vibrationally stable, the lack of single successful synthesis of a new species on the macroscale is surprising, except the scanty reports on the synthesis of N1+ , N4 , and N10 5 by American and Japanese researchers. The discovery of N1+ has opened up new vistas in research and de5 velopment activities on polynitrogen compounds. The imagination-driven route for N60 synthesis may come to reality in the near future. Such a molecule conned to a specic geometrical shape is the prime candidate to fuel supersonic transport vehicles. Because of the nature of nitrogen bonding, the explosive power of these unusual compounds will be stunning. If it is possible to realize polynitrogens in large amounts, they can drastically change the technologies of high-energy rocket propellants and explosives. Despite the proven worth of advanced HEMs, AP- and HMX-based systems still dominate. Compatibility problems of novel HEMs with other propellant components need to be tackled. Ultra-

high power materials are conceptualized to meet future demands. However, novel technologies need to be mastered to bring such materials into realm. A major technological breakthrough is needed to economically justify obtaining of new HEMs. The authors are grateful to Dr. T. Mukundan for his suggestions. The authors also acknowledge the assistance received from H. Muthurajan (Armament Research and Development Establishment, Pune) in preparation of this manuscript.

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