Inter- and Intramolecular Bonding in 1,3,5-Triamino-2,4,6-trinitrobenzene: An Experimental and Theoretical Quantum Theory of Atoms in Molecules (QTAIM) Analysis

Chua, Zhijie; Gianopoulos, Christopher G.; Zarychta, Bartosz; Zhurova, Elizabeth A.; Zhurov, Vladimir V.; Pinkerton, A. Alan

doi:10.1021/acs.cgd.7b00674

Cited by 25 publications

(42 citation statements)

References 56 publications

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“…Topological analysis of the ED and its derivatives in turn allows unparalleled quantitative insight into intra-and intermolecular bonding in the crystalline state. In recent studies, we experimentally quantified the intermolecular bonding in the insensitive EMs, TATB 15 and TKX-50, 16 corroborating and quantifying the layer motifs widely discussed as a significant contributing factor to their mechanical stabilities. Furthermore, these provided experimental comparison for the quality of various theoretical studies of those compounds.…”

Section: ■ Introductionsupporting

confidence: 66%

QTAIM Assessment of the Intra- and Intermolecular Bonding in a Bis(nitramido–oxadiazolate) Energetic Ionic Salt at 20 K

et al. 2018

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Accurate experimental determination of the electron density distribution for the energetic ionic salt bis(ammonium) 2,2′-dinitramido-5,5′-bis(1-oxa-3,4-diazolate) dihydrate (1) is obtained from multipole modeling of single-crystal X-ray diffraction data collected at 20 K. The intra- and intermolecular bonding is assessed in terms of the quantum theory of atoms in molecules (QTAIM) with a view to better understanding the physicochemical properties in relation to chemical bonding. Topological analysis reveals stronger bonding for the N–NO2 bond relative to energetic nitramines RDX and HMX and the indication of a trend between this and impact sensitivity of nitro-containing energetic materials is noted. The intermolecular bonding of 1 is dominated by classical H-bonds but includes multiple π-bonding interactions and interactions between H-bond donor and acceptor atoms where bond paths are deflected by H atoms. There also exists a weak O···O interaction between end-on nitro groups, as well as an intramolecular ring-forming 1,5-type interaction. An anharmonic description of thermal motion was required to obtain the best fitting model, despite the low temperature of the study. The experimental study was complemented by periodic boundary DFT calculations at the experimental geometry as well as gas phase calculations on the isolated dianion.

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Section: ■ Introductionsupporting

confidence: 66%

QTAIM Assessment of the Intra- and Intermolecular Bonding in a Bis(nitramido–oxadiazolate) Energetic Ionic Salt at 20 K

et al. 2018

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“…Fragments for each non-hydrogen atom in DUBWAB. (Scheuermann et al, 2015), QEPCOG (Pe ´charman et al, 2017), QQQCIG17 (Jorgensen et al 2014), SEDJOC (Venter et al, 2012), SEFSIF11 (Nassour et al, 2014), SIFBAN (Mills et al, 2018), SUJDUZ (Dı ´az-Peralta et al, 2020), TATNBZ03 (Chua et al, 2017), TPHSIL02 (Hupf et al, 2019), XUGSEA (Tan & Tiekink, 2020), XYLTOL03 (Madsen et al, 2004), YULKIC (Arnett & Agapie, 2020) APPENDIX B Example of fragmentation with model ( 2)…”

Section: Discussionmentioning

confidence: 99%

Fragmentation and transferability in Hirshfeld atom refinement

Chodkiewicz¹,

Pawlędzio²,

Woińska³

et al. 2022

IUCrJ

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Hirshfeld atom refinement (HAR) is one of the most effective methods for obtaining accurate structural parameters for hydrogen atoms from X-ray diffraction data. Unfortunately, it is also relatively computationally expensive, especially for larger molecules due to wavefunction calculations. Here, a fragmentation approach has been tested as a remedy for this problem. It gives an order of magnitude improvement in computation time for larger organic systems and is a few times faster for metal–organic systems at the cost of only minor differences in the calculated structural parameters when compared with the original HAR calculations. Fragmentation was also applied to polymeric and disordered systems where it provides a natural solution to problems that arise when HAR is applied. The concept of fragmentation is closely related to the transferable aspherical atom model (TAAM) and allows insight into possible ways to improve TAAM. Hybrid approaches combining fragmentation with the transfer of atomic densities between chemically similar atoms have been tested. An efficient handling of intermolecular interactions was also introduced for calculations involving fragmentation. When applied in fragHAR (a fragmentation approach for polypeptides) as a replacement for the original approach, it allowed for more efficient calculations. All of the calculations were performed with a locally modified version of Olex2 combined with a development version of discamb2tsc and ORCA. Care was taken to efficiently use the power of multicore processors by simple implementation of load-balancing, which was found to be very important for lowering computational time.

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“…Although the correction for harmonic contamination is generally small, it is especially important for weak low-angle reflections, e.g. see the case of triaminotrinitrobenzene, wherein inclusion of the over-estimated, uncorrected 001 and 003 reflections in the original data set were responsible for unreasonable polarization of the electron density perpendicular to the molecular plane (Chua et al, 2017a).…”

Section: Figurementioning

confidence: 99%

Charge densities in actinide compounds: strategies for data reduction and model building

Gianopoulos

Zhurov

Pinkerton

2019

Int Union Crystallogr J

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The data quality requirements for charge density studies on actinide compounds are extreme. Important steps in data collection and reduction required to obtain such data are summarized and evaluated. The steps involved in building an augmented Hansen–Coppens multipole model for an actinide pseudo-atom are provided. The number and choice of radial functions, in particular the definition of the core, valence and pseudo-valence terms are discussed. The conclusions in this paper are based on a re-examination and improvement of a previously reported study on [PPh4][UF6]. Topological analysis of the total electron density shows remarkable agreement between experiment and theory; however, there are significant differences in the Laplacian distribution close to the uranium atoms which may be due to the effective core potential employed for the theoretical calculations.

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Inter- and Intramolecular Bonding in 1,3,5-Triamino-2,4,6-trinitrobenzene: An Experimental and Theoretical Quantum Theory of Atoms in Molecules (QTAIM) Analysis

Cited by 25 publications

References 56 publications

QTAIM Assessment of the Intra- and Intermolecular Bonding in a Bis(nitramido–oxadiazolate) Energetic Ionic Salt at 20 K

QTAIM Assessment of the Intra- and Intermolecular Bonding in a Bis(nitramido–oxadiazolate) Energetic Ionic Salt at 20 K

Fragmentation and transferability in Hirshfeld atom refinement

Charge densities in actinide compounds: strategies for data reduction and model building

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