An Investigation of KS-DFT Electron Densities used in Atoms-in-Molecules Studies of Energetic Molecules

Yau, Anthony D.; Byrd, Edward F. C.; Rice, Betsy M.

doi:10.1021/jp9010845

Cited by 38 publications

(44 citation statements)

References 47 publications

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“…They have found that the number of cps between various atomic basins in each of these compounds do not change changing the size/quality of the basis set or of the DFT potentials. However, this was not true for the 1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX), hexanitrobenzene (HNB), and TATB dimers as there were significant variations in the number of cps because the KS‐DFT wavefunctions have produced significant variations in the topologies of the electron density in the low density regions for these species . Besides the above, there are also a limited number of other isolated compounds that are reported to suffer from this dilemma.…”

Section: Resultsmentioning

confidence: 99%

Hexahalogenated and their mixed benzene derivatives as prototypes for the understanding of halogen···halogen intramolecular interactions: New insights from combined DFT, QTAIM‐, and RDG‐based NCI analyses

Varadwaj

Jin

2015

J Comput Chem

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A large number of fully halogenated benzene derivatives containing the fluorine, chlorine, bromine, and iodine atoms have been experimentally synthesized both as single- and co-crystals (e.g., Desiraju et al., Chem. Eur. J. 2006, 12, 2222), yet the natures of the halogen ··· halogen interactions between the vicinal halogens in these compounds within the intramolecular domain are undisclosed. Given a fundamental understanding of these interactions is incredibly important in many areas of chemical, biological, supramolecular, and material sciences, we present here our newly discovered theoretical results that delineate whilst the nature of an F···F interaction in a pair of two adjacent fluorine atoms in either of the hexafluorobenzene and 1,4-dibromotetrafluorobenzene compounds examined is almost unclear, each of the latter three hexahalogenated benzene derivatives (viz., C6 Cl6 , C6 Br6 , and C6 I6 ), and each of the seven of their fully mixed hexahalogenated benzene analogues, are found to be stabilized by means of a number of halogen···halogen interactions, each a form of long-range attraction within the intramolecular domain. The Molecular Electrostatic Surface Potential model was found to be unsurprisingly unsuitable in unraveling any of the aforesaid attractions between the halogen atoms. However, such interactions successfully enunciated by a set of noncovalent interaction descriptors of geometrical, topological, and electrostatic origins. These latter properties were extracted combining the results of the Density Functional Theory electronic structure calculations with those revealed from Atoms in Molecules, and Reduced Density Gradient charge density-based topological calculations, and are expounded in detail to formalize the conclusions. © 2015 Wiley Periodicals, Inc.

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Section: Resultsmentioning

confidence: 99%

Hexahalogenated and their mixed benzene derivatives as prototypes for the understanding of halogen···halogen intramolecular interactions: New insights from combined DFT, QTAIM‐, and RDG‐based NCI analyses

Varadwaj

Jin

2015

J Comput Chem

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“…Those authors investigated, among others properties, the correlation of sensitivity to impact with different molecular properties such as electrostatic potential, CNO 2 and NNO 2 bond strengths, and molecular and crystalline factors (lattice free space and maximum heat of detonation per unit of volume) . Other researchers also sought to establish correlations between sensitivity and molecular surface electrostatic potentials and bond dissociation energies including applications of the atoms‐in‐molecules partition method . Use of basic properties, such as structural and molecular parameters, and atomic and molecular weights, has been the approach by Keshavarz and collaborators .…”

Section: Introductionmentioning

confidence: 99%

On the molecular origin of the sensitivity to impact of cyclic nitramines

Oliveira

Borges

2018

Int J of Quantum Chemistry

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Nitramine explosives can combine relative insensitivity to initiation and great energy content. In this work, based on a previous approach developed for nitroaromatic explosives, we propose four mathematical models to correlate impact sensitivity, given by the h50 value, to molecular charge properties. Fourteen cyclic nitramines were studied using Density Functional Theory (DFT). Six molecules of the set have measured h50 values, which were used to evaluate the sensitivity models. Converged DFT charge densities of the molecules were partitioned and analyzed according to the distributed multipole analysis (DMA) atom‐centered method. The sensitivity models were based on the DMA electric multipole values. The electron withdrawing role of the nitro group and the strong polarization of the charges of the nitrogen atom in the amine group were clearly identified. The influence of the electronic properties on the sensitivity of the explosives was characterized by including in the sensitivity models the charge values of the nitro or the nitramine groups and electron delocalization, the latter quantified by the DMA quadrupole values of the ring atoms. Inclusion of electron delocalization effects can improve the prediction of h50 values for two out of the five strained‐ring nitramines in the set. The charge values of the nitramine groups are the most important molecular property affecting the impact sensitivity. The h50 values of eight nitramine explosives of the set not available experimentally were computed.

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“…The atoms-in-molecules (AIM) theory [59] was suggested for understanding of the chemical stability by means of stationary properties of the electron density. To assess the applicability of this method for establishing such correlations with various performance and vulnerability properties of energetic materials, subsequent AIM data were calculated from density functional theory wave functions using the B3LYP, PBE and PW91 functionals as well as HartreeFock (HF).…”

Section: Calculations Of Physico-chemical Datamentioning

confidence: 99%

2,2-Dinitroethene-1,1-Diamine

Šimková¹,

Liška²,

Ludvı́k³

2011

COC

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2,2-Dinitroethene-1,1-diamine (FOX-7) is a compound synthesized in 1998 with a simple structure but very unusual properties. One part of the molecule bears two geminal electron-withdrawing nitro groups as a strong oxidation center and the opposite part is represented by two electron-donating amino groups. This combination creates a so called push-pull effect of electrons. The electron distribution is unbalanced enabling intramolecular electron transfer reactions, what is typical for energetic material. Many studies appeared during last decade dealing with synthesis, physical properties, solubility, spectroscopic properties, acidobasic and redox properties, X-ray structure studies, reactivity, thermochemical properties, analytical reactions, quantum chemical calculations, energetic properties etc. The presented review article gives an overview of the papers devoted to the title compound.

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An Investigation of KS-DFT Electron Densities used in Atoms-in-Molecules Studies of Energetic Molecules

Cited by 38 publications

References 47 publications

Hexahalogenated and their mixed benzene derivatives as prototypes for the understanding of halogen···halogen intramolecular interactions: New insights from combined DFT, QTAIM‐, and RDG‐based NCI analyses

Hexahalogenated and their mixed benzene derivatives as prototypes for the understanding of halogen···halogen intramolecular interactions: New insights from combined DFT, QTAIM‐, and RDG‐based NCI analyses

On the molecular origin of the sensitivity to impact of cyclic nitramines

2,2-Dinitroethene-1,1-Diamine

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