Extensive theoretical studies of a new energetic material: Tetrazino‐tetrazine‐tetraoxide (TTTO)

[1,2,3,4]Tetrazino‐[5,6‐e]‐[1,2,3,4]tetrazine‐[1,3,5,7]tetraoxide (TTTO, C2N8O4) was suggested to be a possible candidate of high energy density materials (HEDM). The most stable conformation of TTTO is a planar structure with C2h symmetry. Using various high‐level ab initio methods including Gaussian‐n, Complete Basis Set, Full Coupled Cluster, and W1U models of chemistry together with density functional theory based models, the enthalpies of formation of TTTO at 0 K and standard state were calculated precisely. Moreover, the rovibrational and nuclear magnetic resonance properties were predicted as well. The solid state TTTO was studied using the crystal packing models with the Dreiding force‐filed and the plane‐wave periodic local‐density approximation density functional theory. Three stable polymorphous cells of TTTO have been found with either P212121 or P21/C symmetry. The high heat of formation (>200 kcal/mol), the high density (>2.0 g/cm3), the planar nonpolar electronic structure, and the perfect oxygen balance lead TTTO be a very promising HEDM with exceptional performance. This work provides the first theoretical support for further experimental synthesis and testing. © 2008 Wiley Periodicals, Inc. J Comput Chem 2009

[1]  M. Plesset,et al.  Note on an Approximation Treatment for Many-Electron Systems , 1934 .

[2]  Krishnan Raghavachari,et al.  Gaussian-2 theory for molecular energies of first- and second-row compounds , 1991 .

[3]  L. Curtiss,et al.  Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation , 1997 .

[4]  R. Bartlett,et al.  A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples , 1982 .

[5]  Krishnan Raghavachari,et al.  GAUSSIAN-3 THEORY USING DENSITY FUNCTIONAL GEOMETRIES AND ZERO-POINT ENERGIES , 1999 .

[6]  Jan M. L. Martin,et al.  TOWARDS STANDARD METHODS FOR BENCHMARK QUALITY AB INITIO THERMOCHEMISTRY :W1 AND W2 THEORY , 1999, physics/9904038.

[7]  Krishnan Raghavachari,et al.  Gaussian-3 theory using reduced Mo/ller-Plesset order , 1999 .

[8]  L. Curtiss,et al.  Gaussian-4 theory. , 2007, The Journal of chemical physics.

[9]  Philip E. Eaton,et al.  Synthesis and Chemistry of 1,3,5,7-Tetranitrocubane Including Measurement of Its Acidity, Formation of o-Nitro Anions, and the First Preparations of Pentanitrocubane and Hexanitrocubane1 , 1997 .

[10]  William D. Mattson,et al.  Computational Aspects of Nitrogen-Rich HEDMs , 2007 .

[11]  C. Breneman,et al.  Determining atom‐centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis , 1990 .

[12]  Betsy M Rice,et al.  Improved prediction of heats of formation of energetic materials using quantum mechanical calculations. , 2006, The journal of physical chemistry. A.

[13]  Walter Bauer,et al.  Spontaneous Assembly of a Schiff Base Tetramacrocycle , 2000 .

[14]  Warren E. Pickett,et al.  Pseudopotential methods in condensed matter applications , 1989 .

[15]  K. I. Rezchikova,et al.  A quantum-chemical study of 1,2,3,4,5,6,7,8-octaazanaphthalene and itsN-oxides , 1999 .

[16]  J. Pople,et al.  Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules , 1971 .

[17]  Martin Head-Gordon,et al.  Quadratic configuration interaction. A general technique for determining electron correlation energies , 1987 .

[18]  Matthew L. Leininger,et al.  PSI3: An open‐source Ab Initio electronic structure package , 2007, J. Comput. Chem..

[19]  Juana Vázquez,et al.  HEAT: High accuracy extrapolated ab initio thermochemistry. , 2004, The Journal of chemical physics.

[20]  L. Curtiss,et al.  Gaussian-3 (G3) theory for molecules containing first and second-row atoms , 1998 .

[21]  Clemens C. J. Roothaan,et al.  New Developments in Molecular Orbital Theory , 1951 .

[22]  G. A. Petersson,et al.  A complete basis set model chemistry. VI. Use of density functional geometries and frequencies , 1999 .

[23]  Zvatopluk Zeman,et al.  New Trends in Research of Energetic Materials , 2004 .

[24]  Girish M. Gore,et al.  Studies on CL-20: The most powerful high energy material , 2003 .

[25]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[26]  Herman L. Ammon,et al.  New Atom/Functional Group Volume Additivity Data Bases for the Calculation of the Crystal Densities of C-, H-, N-, O-, F-, S-, P-, Cl-, and Br-Containing Compounds , 2001 .

[27]  T. Dunning,et al.  Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions , 1992 .

[28]  S. L. Mayo,et al.  DREIDING: A generic force field for molecular simulations , 1990 .

[29]  Michael A. Robb,et al.  Application of unitary group methods to configuration interaction calculations , 1979 .

[30]  Michael J. Frisch,et al.  Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets , 1984 .

[31]  Peter Pulay,et al.  Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations , 1990 .

[32]  Nathan J DeYonker,et al.  The correlation-consistent composite approach: application to the G3/99 test set. , 2006, The Journal of chemical physics.

[33]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[34]  Angela K. Wilson,et al.  Gaussian basis sets for use in correlated molecular calculations. IX. The atoms gallium through krypton , 1993 .

[35]  Peter Politzer,et al.  RELATIONSHIPS BETWEEN LATTICE ENERGIES AND SURFACE ELECTROSTATIC POTENTIALS AND AREAS OF ANIONS , 1998 .

[36]  B. Rice,et al.  A quantum mechanical investigation of the relation between impact sensitivity and the charge distribution in energetic molecules , 2002 .

[37]  John A. Montgomery,et al.  A complete basis set model chemistry. V. Extensions to six or more heavy atoms , 1996 .

[38]  Henry F. Schaefer,et al.  A systematic study of molecular vibrational anharmonicity and vibration-rotation interaction by self-consistent-field higher-derivative methods. Linear polyatomic molecules , 1990 .

[39]  Branko Ruscic,et al.  High-accuracy extrapolated ab initio thermochemistry. III. Additional improvements and overview. , 2008, The Journal of chemical physics.