Cubane Pyrolysis: Scaling Bond Polarity with Universal Polynomials DOI Creative Commons
Leandro Ayarde‐Henríquez, Cristian Guerra, Eduardo Chamorro

и другие.

Опубликована: Авг. 16, 2024

This study meticulously examines the criteria for assigning electron rearrangements along intrinsic reaction coordinate (IRC) leading to bond formation and breaking processes during pyrolytic isomerization of cubane (CUB) 1,3,5,7 cyclooctatetraene (COT) from both thermochemical bonding perspectives. The computed gas phase activation enthalpies obtained using state-of-the-art DFT functionals strongly align with experimental values. Notably, no cusp-type function was detected in initial thermal conversion step CUB bicyclo[4.2.0]octa 2,4,7 triene ( as evidenced by examining modulus Hessian determinant at all potentially degenerate critical points (CPs) their relative distances. Contrary previous reports, relevant fluxes pairing density must be described terms fold unfolding. transannular ring opening second highlights characteristics indicative a catastrophe, facilitating direct comparison features. fact underscores role symmetry persistence near topographical events determining type bifurcation. A cusp unified model scaling polarity chemical bonds is proposed, integrating ubiquitous classes such isomerization, bimolecular nucleophilic substitution, cycloaddition. analysis reveals that index (BPI) values within [0, 10-5] au interval correlate unfolding, whereas spans over broader [10-3, ∞) spectrum. These insights emphasize polynomial suitable describing involving symmetric distributions, particularly those homolytic cleavages; contrast, characterizes most elucidated accurately captures COT stepwise mechanism, illustrated sequence catastrophes ELF topology changes IRC. rigorous application BET identifying unfoldings describe crucial are highlighted essential understanding predicting reactivity.

Язык: Английский

Cubane Pyrolysis: Scaling Bond Polarity with Universal Polynomials DOI Creative Commons
Leandro Ayarde‐Henríquez, Cristian Guerra, Eduardo Chamorro

и другие.

Опубликована: Авг. 16, 2024

This study meticulously examines the criteria for assigning electron rearrangements along intrinsic reaction coordinate (IRC) leading to bond formation and breaking processes during pyrolytic isomerization of cubane (CUB) 1,3,5,7 cyclooctatetraene (COT) from both thermochemical bonding perspectives. The computed gas phase activation enthalpies obtained using state-of-the-art DFT functionals strongly align with experimental values. Notably, no cusp-type function was detected in initial thermal conversion step CUB bicyclo[4.2.0]octa 2,4,7 triene ( as evidenced by examining modulus Hessian determinant at all potentially degenerate critical points (CPs) their relative distances. Contrary previous reports, relevant fluxes pairing density must be described terms fold unfolding. transannular ring opening second highlights characteristics indicative a catastrophe, facilitating direct comparison features. fact underscores role symmetry persistence near topographical events determining type bifurcation. A cusp unified model scaling polarity chemical bonds is proposed, integrating ubiquitous classes such isomerization, bimolecular nucleophilic substitution, cycloaddition. analysis reveals that index (BPI) values within [0, 10-5] au interval correlate unfolding, whereas spans over broader [10-3, ∞) spectrum. These insights emphasize polynomial suitable describing involving symmetric distributions, particularly those homolytic cleavages; contrast, characterizes most elucidated accurately captures COT stepwise mechanism, illustrated sequence catastrophes ELF topology changes IRC. rigorous application BET identifying unfoldings describe crucial are highlighted essential understanding predicting reactivity.

Язык: Английский

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