Noncovalent intermolecular energetics: RDX crystal

Politzer, Peter; Ma, Yan

doi:10.1002/qua.20237

Cited by 16 publications

(11 citation statements)

References 26 publications

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“…Our predicted for the interlocked pair was * int E about −8 kcal/mole, and −2 to −3 kcal/mole for the interaction between interlocked pairs [22]. These values are very similar to what we obtained for the corresponding E es , approximately −8 and −3 kcal/mole.…”

Section: Applicationssupporting

confidence: 77%

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Electronic Density Approaches to the Energetics of Noncovalent Interactions

Politzer

2004

IJMS

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Abstract:We present an overview of procedures that have been developed to compute several energetic quantities associated with noncovalent interactions. These formulations involve numerical integration over appropriate electronic densities. Our focus is upon the electrostatic interaction between two unperturbed molecules, the effect of the polarization of each charge distribution by the other, and the total energy of interaction. The expression for the latter is based upon the Hellmann-Feynman theorem. Applications to a number of systems are discussed; among them are dimers of uracil and interacting pairs of molecules in the crystal lattice of the energetic compound RDX.

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Section: Applicationssupporting

confidence: 77%

“…Finally, we investigated the intermolecular interactions in the crystal lattice of RDX (2, hexahydro-1,3,5-trinitro-s-triazine) [22], which is of considerable interest as an important energetic compound. RDX is frequently the subject of molecular dynamics simulations [11,23], which generally obtain E es by a point-charge approximation.…”

Section: Applicationsmentioning

confidence: 99%

Electronic Density Approaches to the Energetics of Noncovalent Interactions

Politzer

2004

IJMS

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“…The space group of the α-HHTT is Pbca : α = β = γ = 90°, a = 13.182 Å, b = 11.574 Å, c = 10.709 Å, and Z = 8. A dimeric α-HHTT structure was built according to previous work. , The significance of this dimer is further discussed in Section 3.3. Geometry optimization and normal-mode harmonic vibrational frequency calculations of the α-HHTT monomer and the chosen dimer in gas phase were performed using the density functional theory (DFT) at the level of B3LYP with the 6-311++G** basis set.…”

Section: Methodsmentioning

confidence: 99%

Ultrafast Intermolecular Vibrational Energy Transfer in Hexahydro-1,3,5-trinitro-1,3,5-triazine in Molecular Crystal by 2D IR Spectroscopy

Shi

Zhao

et al. 2020

J. Phys. Chem. C

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Cyclic nitramine hexahydro-1,3,5-trinitro-s-triazine (HHTT) is an important energetic molecule with a variety of applications. In this work, structural dynamics and vibrational-energy transfer dynamics of HHTT were investigated using steady-state infrared (IR), femtosecond time-resolved IR, and two-dimensional (2D) IR spectroscopic methods. Two different structural forms of HHTT (isolated molecules dissolved in DMSO and microcrystal dispersed in paraffin oil) were examined using the NO2 asymmetric stretching mode as a structural marker. Both intra- and intermolecular vibrational energy transfers were observed in HHTT microcrystal, where the well-known α-conformation was retained. However, less perfect α-HHTT species was found in DMSO. An intermolecular energy dissipation pathway was found to be related to Davydov splitting in the microcrystal form of HHTT, which originates from intermolecular interactions (e.g., electrostatic and hydrogen bonds). Experimental results were supported by quantum-chemistry computations. In addition, both vibrational excited-state relaxation and vibrational energy-transfer processes were found to be more efficient in HHTT microcrystal than in the solvated form. Our work provides a chemical-bond level of insight into the nitro group-containing energetic materials.

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“…In the α-polymorph, the RDX ring takes on a chair conformer with two of the NO2 groups pointed axially and the third NO2 group oriented orthogonally along the equatorial direction 19,20 (other polymorphs are characterized by different NO2 group orientations) with the crystalline unit cell qualitatively described as a quartet of dimers linked through adjacent N⋯O interactions. 21,22 Cleavage of an N-N bond and the production of various nitrogen-containing products (e.g. NO2, HNO, HONO) have been observed from thermal- [23][24][25] and shock-excited 26 samples and are thought be one of the first chemical steps in RDX initiation.…”

Section: Introductionmentioning

confidence: 99%

Mode-Selective Vibrational Energy Transfer Dynamics in 1,3,5-Trinitroperhydro-1,3,5-Triazine (RDX) Thin Films

Cole-Filipiak¹,

Knepper²,

Wood³

et al. 2021

Preprint

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Herein, we report on the sub-picosecond to sub-nanosecond vibrational energy transfer (VET) dynamics of the solid energetic material 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) using broadband, ultrafast infrared transient absorption spectroscopy. Experiments reveal VET occurring on three distinct timescales: sub-picosecond, 5 ps, and 200 ps. The ultrafast appearance of signal at all probed modes in the mid-infrared suggests strong anharmonic coupling of all vibrations in the solid whereas the long-lived evolution demonstrates that VET is incomplete, and thus thermal equilibrium is not attained, even on the hundred picosecond timescale. Mode-selectivity of the longest dynamics suggests coupling of the N–N and axial NO<sub>2</sub> stretching modes with the long-lived, excited phonon bath.

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Noncovalent intermolecular energetics: RDX crystal

Cited by 16 publications

References 26 publications

Electronic Density Approaches to the Energetics of Noncovalent Interactions

Electronic Density Approaches to the Energetics of Noncovalent Interactions

Ultrafast Intermolecular Vibrational Energy Transfer in Hexahydro-1,3,5-trinitro-1,3,5-triazine in Molecular Crystal by 2D IR Spectroscopy

Mode-Selective Vibrational Energy Transfer Dynamics in 1,3,5-Trinitroperhydro-1,3,5-Triazine (RDX) Thin Films

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