Revisiting the bonding evolution theory: a fresh perspective on the ammonia pyramidal inversion and bond dissociations in ethane and borazane

Ayarde-Henríquez, Leandro; Guerra, Cristian; Duque-Noreña, Mario; Chamorro, Eduardo

doi:10.1039/d3cp03572g

Cited by 5 publications

(15 citation statements)

References 111 publications

(230 reference statements)

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“…More importantly, this result aligns perfectly with recent findings. [31][32][33][34][35] These observations highlight the underlying role of density symmetry in controlling the production of ions and radicals along a reactive coordinate, significantly supporting our working hypothesis.…”

Section: Introductionsupporting

confidence: 71%

“…ELF maxima accurately correlate with predictions from the valenceshell electron pair repulsion theory (VSEPR), 47 thus providing a solid connection to Lewis bonding ideas in terms of valence, bonds, core, and lone pairs concepts. 48,49 The topographical analysis of ELF is independent of the theoretical level of theory, 31,33,50,51 and remarkably, such a function has also been approximately obtained https://doi.org/10.26434/chemrxiv-2023-kjrbc-v4 ORCID: https://orcid.org/0000-0001-5963-6028 Content not peer-reviewed by ChemRxiv. License: CC BY-NC-ND 4.0 from electron densities derived from X-ray diffraction data.…”

Section: Theory and Computational Detailsmentioning

confidence: 99%

“…License: CC BY-NC-ND 4.0 description of electron reorganization along the intrinsic reaction coordinate (IRC) is radically different from previous observations. 27 We detected indicators of only one cusp by following a recent easy-to-follow strategy, 31 suggesting that most electron rearrangements have been mischaracterized. More importantly, this result aligns perfectly with recent findings.…”

Section: Introductionmentioning

confidence: 98%

“…Recent advancements in the rigorous application of BET have evidenced that describing relevant chemical events along a reactive coordinate by visually inspecting the ELF topography leads to erroneous assigning of the unfolding characterizing electronic rearrangements. 31 To avoid arbitrary choices and misinterpretations, it is essential to carefully assess local curvature metrics, such as the Hessian matrix at potentially degenerate CPs, and to monitor the variation in distance between them. Adopting this analysis as a standard practice helps minimize ambiguities in assigning and characterizing the specific unfolding that features the topological change.…”

Section: Introductionmentioning

confidence: 99%

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Cubane Pyrolysis: Scaling Bond Polarity with Universal Polynomials

Ayarde Henríquez,

Guerra,

Chamorro

2024

Preprint

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This study presents a novel methodological approach to elucidate the intricate multi-correlation between electron reorganizations, the most stable molecular configurations, and the topographical description of relevant chemical processes. In such a context, an in-depth reevaluation of the chemical bonding analysis underpinning the cubane pyrolysis mechanism, as reported by Seif et al. [RSC Adv., 2020, 10, 32730-32739] is achieved. A fold-cusp unified model of universal functions for scaling bond polarity is derived from this multi-nexus. The scaling revealed that bond polarity index values within the interval [0, 10-5] au correspond to the cusp unfolding, while the fold spans over a wider interval, [10-3, ∞) au. Contrary to previous observations, no cusp flag was detected upon re-examining single scissions and double formations/breakages of carbon-carbon bonds in the first step of the reaction mechanism (i.e., cubane to bicyclo[4.2.0]octa-2,4,7-triene), as demonstrated by the determinant of the Hessian matrix at all potentially degenerate critical points of the electron localization function along the intrinsic reaction coordinate. The transannular ring opening in the second elementary reaction (bicyclo[4.2.0]octa-2,4,7-triene to 1,3,5,7-cyclooctatetraene) is the only chemical process exhibiting cusp characteristics, underscoring the model’s reliability. The computed thermochemical dataset closely matches the experimental values, highlighting the robustness and accuracy of the derived insights.

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Section: Introductionsupporting

confidence: 71%

Section: Theory and Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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Cubane Pyrolysis: Scaling Bond Polarity with Universal Polynomials

Ayarde Henríquez,

Guerra,

Chamorro

2024

Preprint

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“…This calculation constitutes a building block for establishing the intricate link between macro-level thermodynamics and micro-level molecular interactions through chemical bonding analysis of ELF. This kind of methodical approach has been broadly applied in both the solid-state and gas-phase to deepen our understanding across different covalent bonding situations, 87,88 proton transfer reactions, 89 C–H bonds activation, 90 phase transition of the 14 group elements, 91 cycloadditions, 92–99 hemiaminals formation, 100,101 photoreactions, 99,102,103 arynes production, 104 computing local and global properties of solids, 105 and deducing linear models for predicting activation enthalpies of organic and organometallic reacting systems. 106…”

Section: Resultsmentioning

confidence: 99%