A kinetically persistent isomer found for pentazole: a global potential energy surface survey

Bo, Xiaoxu; Zheng, Haifeng; Xin, Jingfan; Ye, Ding

doi:10.1039/c8cc09626k

Cited by 15 publications

(11 citation statements)

References 44 publications

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“…Bond distances only changed by 0.002 Å at most, and bond angles were identical to 0.1° (see Table S1). Our geometries also did not qualitatively differ from previously reported geometries. ,, …”

Section: Resultssupporting

confidence: 61%

“…Bo et al report barrier heights for pentazole decomposition in a study of the global potential energy surface of N 5 H using the composite methods CBS−QB3 (19.16 kcal mol −1 ), G4 theory (18.87 kcal mol −1 ), and W1BD (19.88 kcal mol −1 ). 36 While these energies seem to agree with Burke and Fazen, their CCSD(T) value likely only included a ZPVE correction, though it is never explicitly stated and can be further improved. These differences, as well as the large range over which they span, pose a significant problem when it comes to investigating kinetic properties such as decomposition rates and half-lives, both important to determining the kinetic stabilities of potential HEDMs.…”

Section: ■ Introductionmentioning

confidence: 64%

“…There is currently no consensus on whether diffuse functions are necessary for pentazole and its derivatives. Many previous studies did not use diffuse functions for their optimizations, 6,30,36,57 and those that did gave no justification for why they were included or necessary. 22,27,31,35 Our reoptimization using the aug-cc-pVTZ Dunning basis set did not result in significant differences of the geometry parameters or the energy relative to the products.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…In this case, the energy reported for the parent pentazole only differed by 0.538 kcal mol –1 , but these energies were calculated with the same level of theory as they were optimized and not with the full treatment of a composite method or CBS extrapolation which would likely exacerbate the difference. Bo et al report barrier heights for pentazole decomposition in a study of the global potential energy surface of N 5 H using the composite methods CBS–QB3 (19.16 kcal mol –1 ), G4 theory (18.87 kcal mol –1 ), and W1BD (19.88 kcal mol –1 ) . While these energies seem to agree with Burke and Fazen, their CCSD(T) value likely only included a ZPVE correction, though it is never explicitly stated and can be further improved.…”

Section: Introductionmentioning

confidence: 99%

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Kinetic Stability of Pentazole

et al. 2021

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The utility of high energy density materials (HEDMs) comes from their thermodynamic properties which arise from specific structural features that contribute to energy storage. Studies of such structural features seek to increase our understanding of these energy storage mechanisms in order to further enhance their properties. High-nitrogen-containing HEDMs are of particular interest because they are less toxic than traditional HEDMs. Pentazole is the largest of the nitrogen rings which has been synthesized and considered for an HEDM; however, few experimental studies exist due to the difficulty involved in the synthesis, and most previous theoretical studies employed composite methods where lower level geometries were used with higher level methods. Here, the decomposition reaction of pentazole is studied. Geometries, fundamental frequencies, and energies for each of the stationary points of the decomposition pathway are computed using ab initio methods up to CCSDT(Q). Decomposition rates are calculated over a range of temperatures using canonical transition state theory in order to determine the kinetic stability of pentazole. Based on the present results, it would be difficult for pentazole to act as an HEDM, requiring temperatures close to 200 K to achieve a suitable level of stability.

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Section: Resultssupporting

confidence: 61%

Section: ■ Introductionmentioning

confidence: 64%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Kinetic Stability of Pentazole

et al. 2021

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“…The connection of each transition state was determined by the intrinsic reaction coordinate (IRC) (Fukui, 1981) calculations. The effectiveness of such isomeric and TS search strategies has been confirmed in study of various small to medium-sized systems (Cui et al, 2011; Gao and Ding, 2012; Tang et al, 2012; Guo et al, 2013a,b, 2014; Zhang and Ding, 2014, 2015; He and Ding, 2016; Xu et al, 2017; Bo et al, 2019).…”

Section: Computational Detailsmentioning

confidence: 89%

Global Isomeric Survey of Elusive Cyclopropanetrione: Unknown but Viable Isomers

Xin

Han

et al. 2019

Front. Chem.

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Despite the great interest in energy storage application, stable neutral C n O n ( n > 1) structures either in thermodynamics or kinetics have yet been largely limited due to the rather high tendency to release the very stable CO molecule. The neutral cyclopropanetrione (C 3 O 3 ) cluster has long remained elusive since no isomer with sufficient kinetic stability has been found either experimentally or theoretically. In this work, we constructed the first global potential energy surface of singlet C 3 O 3 at the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ level, from which the kinetic stability of a wide range of C 3 O 3 isomers can be determined by investigating their isomerization and fragmentation pathways. Amongst, a three-membered ring structure 01 is the global C 3 O 3 isomer with a barrier of 10.6 kcal/mol at the sophisticated W1BD level. In particular, two carbene-type isomers 02 and 04 possess appreciable destruction barriers of 20.3 and 24.7 kcal/mol at W1BD, respectively. Thus, 02 and 04 can be useful building blocks for constructing larger high-energy density carbon-oxygen clusters. Moreover, with the carbene center, both might effectively functionalize various nano-materials while retaining the electrochemical active carbonyl and epoxyl moieties that are very desirable in alkali metal-ion batteries.

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Mono‐silicon isoelectronic replacement in CAl₄: van't hoff/le bel carbon or not?

Zheng

2019

J Comput Chem

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In cluster studies, the isoelectronic replacement strategy has been successfully used to introduce new elements into a known structure while maintaining the desired topology. The well-known penta-atomic 18 valence electron (ve) species CAl 2 − 4 and its Al − /Si or Al/Si + isoelectronically replaced clusters CAl 3 Si − , CAl 2 Si 2 , CAlSi − 3 , and CSi 2 + 4 , all possess the same anti-van't Hoff/Le Bel skeletons, that is, nontraditional planar tetracoordinate carbon (ptC) structure. In this article, however, we found that such isoelectronic replacement between Si and Al does not work for the 16ve-CAl 4 with the traditional van't Hoff/Le Bel tetrahedral carbon (thC) and its isoelectronic derivatives CAl 3 X (X = Ga/In/Tl). At the level of CCSD(T)/ def2-QZVP//B3LYP/def2-QZVP, none of the global minima of the 16ve mono-Si-containing clusters CAl 2 SiX + (X = Al/Ga/In/Tl) maintains thC as the parent CAl 4 does. Instead, X = Al/Ga globally favors an unusual ptC structure that has one long C─X distance yet with significant bond index value, and X = In/Tl prefers the planar tricoordinate carbon. The frustrated formation of thC in these clusters is ascribed to the C Si bonding that prefers a planar fashion. Inclusion of chloride ion would further stabilize the ptC of CAl 2 SiAl + and CAl 2 SiGa + . The unexpectedly disclosed CAl 2 SiAl + and CAl 2 SiGa + represent the first type of 16ve-cationic ptCs with multiple bonds.

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A kinetically persistent isomer found for pentazole: a global potential energy surface survey

Abstract: After the pentazole with a 103-year-old research history, the second N5R isomer with reasonable kinetic stability was found computationally.

Cited by 15 publications

References 44 publications

Kinetic Stability of Pentazole

Kinetic Stability of Pentazole

Global Isomeric Survey of Elusive Cyclopropanetrione: Unknown but Viable Isomers

Mono‐silicon isoelectronic replacement in CAl₄: van't hoff/le bel carbon or not?

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A kinetically persistent isomer found for pentazole: a global potential energy surface survey

Abstract: After the pentazole with a 103-year-old research history, the second N5R isomer with reasonable kinetic stability was found computationally.

Cited by 15 publications

References 44 publications

Kinetic Stability of Pentazole

Kinetic Stability of Pentazole

Global Isomeric Survey of Elusive Cyclopropanetrione: Unknown but Viable Isomers

Mono‐silicon isoelectronic replacement in CAl4: van't hoff/le bel carbon or not?

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Mono‐silicon isoelectronic replacement in CAl₄: van't hoff/le bel carbon or not?