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arXiv · 2312.16667

QCT study of the vibrational and translational role in the CN(v) + C2H6(ν1, ν2, ν5 and ν9) reactions

Joaquin Espinosa-Garcia·Cipriano Rangel·Jose C. Corchado
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Abstract

Quasi-classical trajectory (QCT) calculations were conducted on the newly developed full-dimensional potential energy surface, PES-2023, to analyse two critical aspects: the influence of vibrational versus translational energy in promoting reactivity, and the impact of vibrational excitation within similar vibrational modes. The former relates to Polanyi's rules, while the latter concerns mode selectivity. Initially, the investigation revealed that independent vibrational excitation by a single quantum of ethane's symmetric and asymmetric stretching modes (differing by only 15 cm-1) yielded comparable dynamics, reaction cross-sections, HCN vibrational product distributions, and scattering distributions. This observation dismisses any significant mode selectivity. Moreover, providing an equivalent amount of energy as translational energy (at total energies of 9.6 and 20.0 kcal/mol) gave rise to slightly lower reactivity compared to putting the same amount of energy as vibrational energy. This effect is more evident at low energies, presenting a counterintuitive scenario in an "early transition state" reaction. Regarding CN vibrational excitation, our calculations revealed that the reaction cross-section remains nearly unaffected by this vibrational excitation, suggesting the CN stretching mode is a spectator mode. The results were rationalized by considering several factors: the strong coupling between different vibrational modes, between vibrational modes and the reaction coordinate, and a significant vibrational energy redistribution within the ethane reactant before collision. This redistribution creates an unphysical energy flow, resulting in the loss of adiabaticity and vibrational memory before the reactants' collision.

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Joaquin Espinosa-Garcia, Cipriano Rangel, Jose C. Corchado. 2023-12-27. QCT study of the vibrational and translational role in the CN(v) + C2H6(ν1, ν2, ν5 and ν9) reactions. https://arxiv.org/abs/2312.16667

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