Resonances in the CH+N2→HCN+N(4S) reaction: The dynamics of a spin-forbidden process

Tamar Seideman

doi:10.1063/1.467550

Resonances in the CH+N₂→HCN+N(⁴S) reaction: The dynamics of a spin-forbidden process

Tamar Seideman^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

32 Scopus citations

Abstract

The dynamics of the CH+N₂(X¹Σ_g ⁺)→HCN+N(⁴S) reaction is studied theoretically for the first time. A simple two-dimensional model is developed, treating the reaction dynamics on the doublet and on the quartet Born-Oppenheimer surfaces of CHN₂ by exact quantum mechanics and the coupling between the two electronic states within first-order perturbation theory. Summation over total angular momentum states is carried out within the J-shifting approximation and the Boltzmann rate constant is computed over the temperature range of interest for combustion T≲1700 K. The reaction probability exhibits a rich resonance pattern, manifesting the existence of long-lived quasibound intermediate states on both the doublet and the quartet surfaces. These resonances affect the dynamics profoundly, being the driving force behind the spin-changing reaction. The thermal rate constant increases with temperature in an Arrhenius type fashion and in qualitative agreement with high-temperature experiments.

Original language	English (US)
Pages (from-to)	3662-3670
Number of pages	9
Journal	The Journal of Chemical Physics
Volume	101
Issue number	5
DOIs	https://doi.org/10.1063/1.467550
State	Published - 1994

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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title = "Resonances in the CH+N2→HCN+N(4S) reaction: The dynamics of a spin-forbidden process",

abstract = "The dynamics of the CH+N2(X1Σg +)→HCN+N(4S) reaction is studied theoretically for the first time. A simple two-dimensional model is developed, treating the reaction dynamics on the doublet and on the quartet Born-Oppenheimer surfaces of CHN2 by exact quantum mechanics and the coupling between the two electronic states within first-order perturbation theory. Summation over total angular momentum states is carried out within the J-shifting approximation and the Boltzmann rate constant is computed over the temperature range of interest for combustion T≲1700 K. The reaction probability exhibits a rich resonance pattern, manifesting the existence of long-lived quasibound intermediate states on both the doublet and the quartet surfaces. These resonances affect the dynamics profoundly, being the driving force behind the spin-changing reaction. The thermal rate constant increases with temperature in an Arrhenius type fashion and in qualitative agreement with high-temperature experiments.",

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N2 - The dynamics of the CH+N2(X1Σg +)→HCN+N(4S) reaction is studied theoretically for the first time. A simple two-dimensional model is developed, treating the reaction dynamics on the doublet and on the quartet Born-Oppenheimer surfaces of CHN2 by exact quantum mechanics and the coupling between the two electronic states within first-order perturbation theory. Summation over total angular momentum states is carried out within the J-shifting approximation and the Boltzmann rate constant is computed over the temperature range of interest for combustion T≲1700 K. The reaction probability exhibits a rich resonance pattern, manifesting the existence of long-lived quasibound intermediate states on both the doublet and the quartet surfaces. These resonances affect the dynamics profoundly, being the driving force behind the spin-changing reaction. The thermal rate constant increases with temperature in an Arrhenius type fashion and in qualitative agreement with high-temperature experiments.

AB - The dynamics of the CH+N2(X1Σg +)→HCN+N(4S) reaction is studied theoretically for the first time. A simple two-dimensional model is developed, treating the reaction dynamics on the doublet and on the quartet Born-Oppenheimer surfaces of CHN2 by exact quantum mechanics and the coupling between the two electronic states within first-order perturbation theory. Summation over total angular momentum states is carried out within the J-shifting approximation and the Boltzmann rate constant is computed over the temperature range of interest for combustion T≲1700 K. The reaction probability exhibits a rich resonance pattern, manifesting the existence of long-lived quasibound intermediate states on both the doublet and the quartet surfaces. These resonances affect the dynamics profoundly, being the driving force behind the spin-changing reaction. The thermal rate constant increases with temperature in an Arrhenius type fashion and in qualitative agreement with high-temperature experiments.

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Resonances in the CH+N₂→HCN+N(⁴S) reaction: The dynamics of a spin-forbidden process

Abstract

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