Molecular orbital study of the electronic structure and spectrum of hexahydro-1,3,5-trinitro-s-triazine

Orloff, M. K.; Mullen, P. A.; Rauch, Francis C.

doi:10.1021/j100909a026

Cited by 44 publications

(26 citation statements)

References 7 publications

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“…The experimental RDX UV spectrum in acetonitrile has two distinct maxima at 5.25 eV and at 6.34 eV, the latter being most intense [8]. This spectrum is shown in Figure 4 along with our RI-CC2/TZ-VPPЈ and TDDFT/TZVPPЈ vacuum results.…”

Section: Resultssupporting

confidence: 59%

The electronically excited states of RDX (hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine): Vertical excitations

Borges

Aquino

Barbatti

et al. 2009

Int J of Quantum Chemistry

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ABSTRACT:The RDX molecule, hexahydro-1,3,5-trinitro-1,3,5-triazine, is a key component for several energetic materials, which have important practical applications as explosives. A systematic study of the electronic excited states of RDX in gas phase using time-dependent density functional theory (TDDFT), algebraic diagrammatic construction through second order method [ADC (2)], and resolution of the identity coupled-cluster singles and doubles method (RI-CC2) was carried out. Transition energies and optical oscillator strengths were computed for a maximum of 40 transitions. RI-CC2 and ADC (2) predict a spectrum shaped by three intense -* transitions, two with charge transfer and one with localized character. TDDFT fails in the description of the charge transfer states. The low-energy band of the experimental UV spectrum of RDX is assigned to the first charge transfer state. Two alternative assignments of the high-energy band are proposed.

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Section: Resultssupporting

confidence: 59%

The electronically excited states of RDX (hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine): Vertical excitations

Borges

Aquino

Barbatti

et al. 2009

Int J of Quantum Chemistry

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“…If this excited state lives longer than characteristic time of nuclear vibrations, then decomposition can certainly occur. The nature of the HOMO to LUMO excitation and its relation to the molecular decomposition has been also established in earlier theoretical 39 and experimental 38 studies. In FIG.…”

Section: Results Of Calculations and Proposed Excitonic Modelmentioning

confidence: 85%

An excitonic mechanism of detonation initiation in explosives

Kuklja

Stefanovich

Kunz

2000

The Journal of Chemical Physics

164

100

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Line-imaging velocimetry for observing spatially heterogeneous mechanical and chemical responses in plastic bonded explosives during impact Rev. Sci. Instrum. 84, 083903 (2013); 10.1063/1.4817307 Band-gap tuning at the strong quantum confinement regime in magnetic semiconductor EuS thin films Appl. Phys. Lett. 100, 211910 (2012); 10.1063/1.4720167Compression-induced effect on the electronic structure of cyclotrimethylene trinitramine containing an edge dislocation A novel mechanism for detonation initiation in solid explosives is proposed. This is based on electronic excitations induced by an impact wave propagating through the crystal. We illustrate the model by using the RDX ͑C 3 H 6 N 6 O 6 ) crystal as an example. In our model, a key role belongs to lattice defects, in particular edge dislocations, which promote dramatic changes in the electronic structure, primarily a reduction of the optical gap due to the splitting off of local electronic states from both valence and conduction bands. The pressure inside the impact wavefront further reduces the band gap, making it close to zero. This promotes highest occupied molecular orbital-lowest unoccupied molecular orbital HOMO-LUMO transitions resulting in N-NO 2 bond breaking and the creation of favorable conditions for the initiation of a chain reaction. Experimental facts supporting the suggested mechanism are discussed.

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“…From this observation one may suggest that the lowest energy electronic excitation, i.e., promotion of an electron from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) may lead to the breaking of the N-NO 2 bond. The nature of the HOMO to LUMO excitation and its relation to the molecular decomposition has also been established in earlier theoretical [92] and experimental [91] studies. The lattice relaxation induced by defects was neglected in this study to reduce computational costs.…”

Section: The Electronic Structure Of Rdx Crystals Containing Edge Dismentioning

confidence: 79%

Modeling Defect-Induced Phenomena

Kuklja

Rashkeev

2009

Static Compression of Energetic Materials

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Elucidation of dissociation mechanisms, energy localization, and transfer phenomena in the course of explosive decomposition of energetic materials (EMs) are central for understanding, controlling, and enhancing the performance of these materials as fuels, propellants, and explosives. Quality of energetic materials is often judged using two main parameters: sensitivity to detonation and its performance. Low sensitivity is desired to make the material relatively stable to external stimuli, i.e., controllable and able of triggering rapid dissociation only when needed and not accidentally. Performance, on the other hand, is to be high to provide larger heat of the explosive reaction. These parameters do not necessarily correlate with each other and depend on many variables such as molecular and crystalline structures, history of samples, the particle size, crystal hardness and orientation, external stimuli, aging, storage conditions, and others. Mechanisms governing performance are fairly well understood whereas mechanisms of sensitivity are poorly known and need to be much more extensively studied. It is widely accepted though that the thermal decomposition reactions of the materials play a significant role in their sensitivity to mechanical stimuli and their explosive properties [1].The decomposition of energetic materials can be initiated with a mechanical impact, thermal heating, a shock wave, or a spark. Such events in solids generate molecules in highly excited vibronic and/or electronic states. Clearly, the decomposition of solid explosives under shock, spark, laser, or plasma ignition must include contributions from both ground and excited electronic states. Excitation in the UV can markedly reduce the power requirements for detonation of some secondary explosives. Therefore, establishing the initial steps of high explosive (HE) decomposition is an important goal to pursue. Decomposition triggered by excited electronic states seems appealing because electronic excitation of the system to an unstable potential energy surface can result in rapid dissociation of a molecule and consequent chain reaction.

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Molecular orbital study of the electronic structure and spectrum of hexahydro-1,3,5-trinitro-s-triazine

Cited by 44 publications

References 7 publications

The electronically excited states of RDX (hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine): Vertical excitations

The electronically excited states of RDX (hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine): Vertical excitations

An excitonic mechanism of detonation initiation in explosives

Modeling Defect-Induced Phenomena

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