| Triazolium-based Energetic Ionic Liquids |
MAR 2005 |
30 pages |
| Authors:
Michael W. Schmidt; Mark S. Gordon; Jerry A. Boatz; IOWA STATE UNIV AMES DEPT OF CHEMISTRY
|
 | The energetic ionic liquids formed by the 1,2,4-triazolium cation family and dinitramide anion are investigated by ab initio quantum chemistry calculations, to address the following questions: How does substitution at the triazolium ring's nitrogen atoms affect its heat of formation, and its charge delocalization? What kind of ion dimer structures might exist? And, do deprotonation reactions occur, as a possible first step in the decomposition of these materials? |
|
| Reaction Chemistry of HN3 with HF, Halogens and Pseudohalogens |
14 JAN 2005 |
28 pages |
| Authors:
William W. Wilson; Karl O. Christie; Jerry A. Boatz; Ralf Haiges; ENGINEERING RESEARCH AND CONSULTING INC(ERC INC) EDWARDS AFB CA
|
| Briefing charts of presentation on the reaction chemistry of HN3 with HF, halogens and pseudohalogens. |
|
| Polyazide Chemistry. Preparation and Characterization of the First Binary Group 6 Azides, Mo(N3)6, W(N3)6, Mo(N3)7- and W(N3)7- and the NW(N3)4- and NMo(N3)4- Ions |
NOV 2004 |
6 pages |
| Authors:
Ralf Haiges; Jerry A. Boatz; Robert Bau; Stefan Schneider; Thorsten Schroer; Muhammed Yousufuddin; Karl O. Christe; AIR FORCE RESEARCH LAB EDWARDS AFB CA SPACE AND MISSILE PROPULSION DIV
|
| Whereas numerous binary transition-metal azido complexes have been reported,1 no binary Group 6 azides are known. Only a limited number of partially azide-substituted molybdenum and tungsten compounds have been reported. Furthermore, no heptaazido compounds have been described. Herein, we report the synthesis and characterization of the first binary Group 6 azides, Mo(N3)6, W(N3)6, Mo(N3)7-, and W(N3)7-. The last two ions represent the first examples of heptaazides. We also report the ... |
|
| Polyazide Chemistry Preparation and Characterization of As(N3)5, Sb(N3)5 and P(C6H5)4Sb(N3)6 |
SEP 2004 |
19 pages |
| Authors:
Ralf Haiges; Jerry A. Boatz; Ashwani Vij; Vandana Vij; Michael Gerken; Stefan Schneider; Thorsten Schroer; Muhammed Yousufuddin; Karl O. Christe; AIR FORCE RESEARCH LAB EDWARDS AFB CA SPACE AND MISSILE PROPULSION DIV
|
| The binary arsenic- and antimony azide species AS(N3)3, As(N3)4+, As(N3)4-, As(N3)6-, Sb(N3)3, Sb(N3)4+, Sb(N3)4- and Sb(N3)6- have previously been reported, and the crystal structures of As(N3)3, Sb(N3)3 and As(N3)6- were determined. In addition, the Lewis based stabilized species M(N3)5-LB (M=As,Sb; LB=pyridine, quinoline NH3, N2H4, NH2CN) were published. However, previous attempts to obtain the neat pentaazides of arsenic and antimony were not successful. Even at low temperatures, attempted syntheses resulted in ... |
|
| First Principles Calculations of the Adsorption of Nitromethane and 1,1- Diamino-2,2-dinitroethylene (FOX-7) Molecules on Al2O3(0001) Surface |
AUG 2004 |
54 pages |
| Authors:
Dan C. Sorescu; Jerry A. Boatz; Donald L. Thompson; AIR FORCE RESEARCH LAB EDWARDS AFB CA SPACE AND MISSILE PROPULSION DIV
|
| First-principles calculations based on density functional theory (DFT) and the generalized gradient approximation (GGA) have been used to study the adsorption of nitromethane (NM) and 1,1-diamino-2,2-dinitroethylene (FOX-7) molecules on the basal plane of an alpha-Al2O3 crystal. The calculations employ a (2x2) supercell slab model and 3D periodic boundary conditions. Based on these calculations we have determined that both NM and FOX-7 molecules can adsorb nondissociatively on the surface with the ... |
|
| Preparation and Characterization of the First Binary Titanium Azides, Ti(N3)4, P(C6H5)4Ti(N3)5 and P(C6H5)42Ti(N3)6 and on Linear Ti-N-NN Coordination |
12 MAR 2004 |
21 pages |
| Authors:
Karl O. Christe; Ralf Haiges; Stefan Schneider; Thorsten Schroer; Jerry A. Boatz; ENGINEERING RESEARCH AND CONSULTING INCHUNTSVILLE AL
|
| Where as numerous partially azide-substituted titanium compounds had previously been reported, 1-7 no binary titanium azides were known. In a recent theoretical study the group 4 metal tetrazides M(N3)4 (M = Ti, Zr, Hf, Th) were predicted 8 to be vibrationally stable exhibiting tetrahedral structures with unique linear M-N-NN bond angles (see Figure 1). All previously characterized covalent binary azide species possess bent M-N-NN angles. In this paper we wish ... |
|
| Methyl Tin(IV) Derivatives of HOTeF5 and HN(SO2CF3)2 |
11 SEP 2003 |
|
| Authors:
Ashwani Vij; William W. Wilson; Vandana Vij; Jerry A. Boatz; Robert C. Corley; AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE
|
|
| Towards New Polynitrogen Species: The Search for Viable Precursors |
31 MAR 2003 |
|
| Authors:
Jerry A. Boatz; Karl Christie; Ralph Haiges; Stefan Schneider; Thorsten Schroer; AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE
|
|
| First-Principles Calculations of the Adsorption of Nitromethane and 1,1- Diamino-2,2-dinitroethylene (FOX-7) Molecules on the Al(111) Surface |
31 MAR 2003 |
33 pages |
| Authors:
Dan C. Sorescu; Jerry A. Boatz; Donald L. Thompson; AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE
|
| First-principles calculations based on spin-polarized density functional theory (DFT) and the generalized gradient approximation (GGA) have been used to study the adsorption of nitromethane (NM) and 1,1-diamino-2,2- dinitroethylene (FOX-7) molecules on the Al(111) surface. The calculations employ (3x3) aluminum slab geometries and 3D periodic boundary conditions. Based on these calculations, we have determined that both dissociative and nondissociative adsorption mechanisms are possible, depending on the molecular orientation and the particular ... |
|
| Synthesis and Characterization of the trans-IO2F5(2-) Dianion |
11 FEB 2003 |
|
| Authors:
Jerry A. Boatz; William J. Casteel Jr.; Karl O. Christe; David A. Dixon; Michel Gerken; AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE WEST
|
 | The combination of CH3CN solutions of N(CH3)4F and a mixture of cis- and trans-N(CH3)4IO2F4 produces the novel trans-IO2F5(2-) anion. Under the given conditions, only the trans-IO2F4(-) anion acts as a fluoride ion acceptor, thus allowing the separation of isomerically pure, soluble cis-IO2F4(-) from insoluble trans-IO2F5(2-). |
|
| Polyazide Chemistry Preparation and Characterization of Te(N3)4 and P(C6H5)42Te(N3)6 |
2003 |
23 pages |
| Authors:
Ralf Haiges; Jerry A. Boatz; Michael Gerken; Stefan Schneider; Thorsten Schroer; ENGINEERING RESEARCH AND CONSULTING INC(ERC INC) EDWARDS AFB CA
|
| The azido-group is highly energetic and adds about 70 kcal/mol to the energy content of a molecule. It is, therefore, not surprising that polyazides are highly endothermic compounds, and that their energy content increases with an increasing number 9f azido ligands. Compared to the relatively stable azide anion, which possesses two double bonds, the bonds in covalent azides are polarized towards a single and a triple bond, which greatly facilitates ... |
|
| First Principles Calculation of the Chemisorption Properties of Nitro- Containing Molecules on the Al(111) Surface (Multiscale Simulations of High Energy Density Materials Challenge Project) |
17 MAY 2002 |
9 pages |
| Authors:
Dan C. Sorescu; Jerry A. Boatz; Donald L. Thompson; AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE WEST
|
| First-principles calculations based on spin-polarized density functional theory (DFT) and the generalized gradient approximation (GGA) have been used to study the adsorption of nitromethane (NM), 1,1-diamino-2,2- dinitroethylene (FOX7) and 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) on Al(111) surface. The calculations employ aluminum slab geometries and 3D periodic boundary conditions. Three surface models have been considered in these studies. |
|
| New Polynitrogen Molecules -- Energetic Air as a Next-Generation Propellant? |
29 APR 2002 |
|
| Authors:
Karl O. Christe; Jerry A. Boatz; AIR FORCE RESEARCH LAB EDWARDS AFB CA SPACE AND MISSILE PROPULSION DIV
|
| The identification, development, and formulation of new energetic materials for advanced rocket propulsion applications is an area of long- standing interest to the Air Force. The performance limits of currently used propellants have been reached, so new energetic compounds are required to significantly improve the ability of the warfighter to access and control space. Polynitrogen species such as the recently discovered N5+ cation are of interest as potential energetic ingredients ... |
|
| Synthesis and Characterization of the SO2N3(-), (SO2)2N3(-), and SO3N3(- ) Anions |
06 MAR 2002 |
51 pages |
| Authors:
Karl O. Christe; Jerry A. Boatz; Michael Gerken; Ralf Haiges; Stefan Schneider; AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE WEST
|
| SO2 solutions of azide anions are bright yellow and their Raman spectra indicate the presence of covalently bound azide. Removal of the solvent at -64 deg C from CsN3 or N(CH3)4N3 solutions produces yellow (SO2)2N3(-) salts. Above -64 deg C, these salts lose one mole of SO2, resulting in white SO2N3 salts that are marginally stable at room temperature and thermally decompose to the corresponding azides and SO2. |
|
| Bond Dissociation Energies of Energetic Compounds: A Comparison of Theoretical Methods |
25 OCT 2000 |
16 pages |
| Authors:
Jerry A. Boatz; Donald L. Thompson; AIR FORCE RESEARCH LAB EDWARDS AFB CA SPACE AND MISSILE PROPULSION DIV
|
| Due to their computational efficiency, density functional methods utilizing semiempirical hybrid functionals such as B3LYP are commonly used in calculating the molecular potential energy surfaces of a wide variety of molecules. In particular, potential energy surfaces of several energetic compounds such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 1,3,3- trinitroazetidine (TNAZ), 5-nitro-2,4-dihydro-3H-1,2,4-triazolone (NTO), and 1, 1-diamino-2,2-dinitroethylene recently have been computed using density functional methods (B3LYP). These potential energy surfaces are used, for example, to ... |
|
| Theory and Synthesis of New High Energy Density Materials |
03 OCT 2000 |
5 pages |
| Authors:
Karl O. Christe; William W. Wilson; Ashwani Vij; Jeffrey A. Sheehy; Jerry A. Boatz; AIR FORCE RESEARCH LAB EDWARDS AFB CA SPACE AND MISSILE PROPULSION DIV
|
| The aim of this AFOSR program is the synthesis of novel HEDM compounds, exploiting the synergism between theory and synthesis. Theoretical calculations are routinely used to guide the synthesis efforts and to facilitate the identification and characterization of the products. |
|
| The Structure of the SO2F Anion, A Problem Case |
19 JUN 2000 |
39 pages |
| Authors:
Paul G. Watson; Tobias Borrmann; Ashwani Vij; Jerry A. Boatz; Karl O. Christe; AIR FORCE RESEARCH LAB EDWARDS AFB CA SPACE AND MISSILE PROPULSION DIV
|
| Recently, room-temperature crystal structures of SO2F(-) in its K(+) and Rb(+) salts were published in Z. Among. Allg. Chem. 1999, 625, 385 and claimed to represent the first reliable geometries for SO2F(-). However, their almost identical 5-O and S-F bond lengths and O-S-O and O-S-F bond angles are in sharp contrast to the results from theoretical calculations. To clarify this discrepancy, the new (CH3)2N3SO(+) and the known N(CM3)4(+), (CH3)2N3S(+) and ... |
|
| New Materials Design |
31 AUG 1999 |
9 pages |
| Authors:
Gregory Voth; Ruth Pachter; Mark S. Gordon; Jerry A. Boatz; AIR FORCE RESEARCH LAB EDWARDS AFB CA SPACE AND MISSILE PROPULSION DIV
|
| Progress has been made on several projects under the Challenge Project award. In the area of high energy density materials, calculations are under way on Al atoms embedded in clusters of H2 molecule. These calculations are very demanding, since very large basis sets and high levels of theory are required to obtain sufficient accuracy for these weakly bound species. Potential energy surfaces are being determined to assess the mobility of ... |
|
| Quantum and Classical Monte Carlo and Molecular Dynamics Simulations of the Structures, Photoionization-Induced Fragmentation, and Optical Absorption Spectra of AlArN Clusters |
27 MAY 1999 |
27 pages |
| Authors:
Jerry A. Boatz; Jeffrey A. Sheehy; Robert J. Hinde; Peter W. Langhoff; AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE WEST
|
| The theory group at AFRL/PRSP is engaged in an ongoing effort to develop, implement, and test the spectral theory of Schrodinger eigenstates for efficient construction of accurate many-body potential energy surfaces for HEDM systems such as atoms embedded in solid hydrogen. Because good experimental data is available for AlAr(sub N) clusters, they make an excellent test bed for the spectral theory and its computational implementation. We have used the spectral ... |
|
| Synthesis of Catenated Polynitrogen Compounds |
27 MAY 1999 |
32 pages |
| Authors:
Karl O. Christe; William W. Wilson; Jerry A. Boatz; Jeffrey A. Sheehy; AIR FORCE RESEARCH LAB EDWARDS AFB CA SPACE AND MISSILE PROPULSION DIV
|
| Presentation includes overview of synthesis of novel compounds consisting of highly endothermic polynitrogen allotropes; use techniques developed in synthesis of other energetic materials to pursue catenated rather than polycyclic polynitrogen compounds; use theory and calculations to guide synthesis efforts; and potential payoffs. |
|
| High Energy Density Materials: Synthesis and Characterization of the Pentanitrogen (1+) Cation, N5+, A Novel Homoleptic Polynitrogen Ion |
12 MAY 1999 |
24 pages |
| Authors:
Karl O. Christe; William W. Wilson; Jeffrey A. Sheehy; Jerry A. Boatz; AIR FORCE RESEARCH LAB EDWARDS AFB CA SPACE AND MISSILE PROPULSION DIV
|
| Polynitrogen compounds are of significant interest as high energy density materials (HEDM) for propulsion or explosive applications. In spite of numerous theoretical studies predicting that certain all-nitrogen compounds might be stable, however, only a few unsuccessful experimental studies aimed at their actual synthesis have been undertaken. |
|
| Experimental and Theoretical Characterization of the Oxygen-Coordinated Donor-Adducts of COCl2, COClF and COF2 with AsF5 and SbF5 |
04 MAR 1999 |
24 pages |
| Authors:
Berthold Hoge; Jerry A. Boatz; Karl O. Christe; AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE WEST
|
| When reacted with an excess of the corresponding carbonyl halides, AsF5 and SbF5 from the following 1:1 adducts: COCl2*AsF5, COCl2*SbF5, COCIF*AsF5, COClF*SbF5, COF2*AsF5 and COF2*SbF5. All adducts are unstable at ambient temperature, and their dissociation enthalpies were determined from the dissociation pressure curves. Vibrational and multinuclear NMR spectra and theoretical calculations show that all compounds are oxygen-coordinated donor- acceptor adducts, and that the strengths of the oxygen-bridges increase from COF2 ... |
|
| Hepta-Coordination. Synthesis and Characterization of the IOF52- Dianion, an XOF5E Compound |
06 JAN 1999 |
16 pages |
| Authors:
Karl O. Christe; William W. Wilson; David A. Dixon; Jerry A. Boatz; AIR FORCE RESEARCH LAB EDWARDS AFB CA SPACE AND MISSILE PROPULSION DIV
|
| The new IOF5(sup 2-) dianion was prepared in the form of its cesium salt by heating stoichiometric amounts of CsF, I2O5 and IF5 to 162 deg C for 14 days. The white stable solid was characterized by vibrational spectroscopy. A normal coordinate analysis was carried out with the help of ab initio calculations at the HF/ECP/DZP level of theory and resulted in an excellent agreement between observed and calculated frequencies. ... |
|
| Theory and Synthesis of New High Energy Density Materials |
30 APR 1998 |
19 pages |
| Authors:
Karl O. Christe; William W. Wilson; Greg W. Drake; Jeff A. Sheehy; Jerry A. Boatz; AIR FORCE RESEARCH LAB EDWARDS AFB CA SPACE AND MISSILE PROPULSION DIV
|
| Efforts are described to combine the NF4+ cation with highly energetic anions, such as NO(2), NO(3), and N(NO2)2. In the case of NO(3), the NO(3) anion was fluorinated already at very low temperatures by NF(4) to give fluorine nitrate in high yield. In the case of NO(2), the reaction with NF(4) yielded an unknown unstable decomposition product in low yield, but the reaction was very difficult to control and consistently ... |
|
| Monte Carlo Simulations of the Structures and Optical Absorption Spectra of AlAr(sub N) Clusters |
30 APR 1998 |
24 pages |
| Authors:
Jerry A. Boatz; Jeffery A. Sheehy; Peter W. Langhoff; AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE WEST
|
| Classical Monte Carlo simulation techniques have been used in conjunction with recently devised spectral methods for constructing the ground and low-lying excited state potential energy surfaces of atomic aggregates to predict the structures and optical absorption spectra of AlAr(sub N) clusters. The new spectral theory properly accounts for the change in electronic state character encountered in avoided crossings of diatomic adiabatic states and of the associated AlAr(sub N) aggregate states, ... |
|
| New Materials Design |
28 APR 1998 |
9 pages |
| Authors:
Gregory Voth; Ruth Pachter; Mark Gordon; Jerry A. Boatz; AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE WEST
|
| Progress has been made on several projects under the Challenge Project award. In the area of high energy density materials, calculations are under way on Al atoms embedded in clusters of 112 molecule. These calculations are very demanding, since very large basis sets and high levels of theory are required to obtain sufficient accuracy for these really bound species. Potential energy surfaces are being determined to assess the mobility of ... |
|
| Theoretical Investigations of HEDM |
24 FEB 1998 |
8 pages |
| Authors:
Jeffrey A. Sheehy; Jerry A. Boatz; Jeffrey D. Mills; Peter W. Langhoff; AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE WEST
|
| The computational and theoretical chemistry group in the Propulsion Sciences Division at the Air Force Research Laboratory (AFRL) is engaged in several projects that support experimental research in the high energy density matter (HEDM) program. The spectral theory of chemical binding continues to be developed and implemented, providing a new framework for constructing adiabatic potential-energy surfaces for aggregates of interacting atomic or molecular species and giving insights into the structural ... |
|
| Pentagonal Planar AX5 Species: Synthesis and Characterization of the Iodine (III) Pentafluoride Dianion, IF5 |
13 JAN 1998 |
26 pages |
| Authors:
Karl O. Christe; William W. Wilson; Greg W. Drake; David A. Dixon; Jerry A. Boatz; AIR FORCE RESEARCH LAB EDWARDS AFB CA PROPULSION DIRECTORATE WEST
|
| The new IF5(2-) dianion, which is5 species, was prepared as its N(CH3)4(+) salt from N(CH3)4IF4 and N(CH3)4F in CH3CN solution. Its structure was established by infrared and Raman spectroscopy, ab initio calculations and a comparison to isoelectronic XeF5(-). Furthermore, vibrational spectroscopy and x-ray powder diffraction data show that the previously reported composition 'Cs3IF6', is actually a mixture of Cs2IF5 and CsF. Ab initio calculations also show that the most probable ... |
|
| Monte Carlo Simulations of the Structures and Optical Absorption Spectra of Na Atoms in Ar Clusters, Surfaces, and Solids; a Detailed Presentation of the Theoretical Methods Used |
JUN 95 |
60 pages |
| Authors:
Jerry A. Boatz; Mario E. Fajardo; PHILLIPS LAB EDWARDS AFB CA
|
| Optical absorption spectra of Na/Ar systems are calculated by combining the classical Monte Carlo simulation method with a quantum mechanical first-order perturbation scheme for estimating the energies of the Na (3p(2P)) excited states. The model incorporates many drastic approximations, but contains no adjustable parameters. Our Na/Ar matrix simulations generated relaxed structures for several candidate trapping sites based on various sized vacancies in fcc solid Ar. Trapping sites for which the ... |
|
| An Initio Studies of Ground and Excited Electronic States of MgAr, CdAr, and BeAr |
26 JUL 91 |
36 pages |
| Authors:
Jerry A. Boatz; Keld L. Bak; Jack Simons; UTAH UNIV SALT LAKE CITY DEPT OF CHEMISTRY
|
| The ground state and several excited state potential energy surfaces for the diatomic molecules MgAr, CdAr, and BeAr have been computed using complete active space self-consistent field (CASSCF) wavefunctions and valence double- and triple-zeta quality basis sets augmented with polarization and diffuse functions. Pump-and-probe laser experiments have examined the quenching of excited singlet states of metal-rare gas complexes such as CdXe to produce triplets that dissociate to 3P sub J ... |
|
Reports by Author
