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Structure, Stability, and Spectroscopic Properties of Small Acetonitrile Cation Clusters

Cerqueira, Henrique B. A., Santos, Julia C., Fantuzzi, Felipe, Ribeiro, Fabio de A., Rocco, Maria Luiza M., Oliveira, Ricardo R., Rocha, Alexandre B. (2020) Structure, Stability, and Spectroscopic Properties of Small Acetonitrile Cation Clusters. Journal of Physical Chemistry A, 124 (34). pp. 6845-6855. ISSN 1089-5639. (doi:10.1021/acs.jpca.0c03529) (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided) (KAR id:98558)

The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided. (Contact us about this Publication)
Official URL:
https://doi.org/10.1021/acs.jpca.0c03529

Abstract

Ionization and fragmentation pathways induced by ionizing agents are key to understanding the formation of complex molecules in astrophysical environments. Acetonitrile (CH3CN), the simplest organic nitrile, is an important molecule present in the interstellar medium. In this work, DFT and MP2 calculations were performed in order to obtain the low energy structures of the most relevant cations formed from electron-stimulated ion desorption of CH3CN ices. Selected reaction pathways and spectroscopic properties were also calculated. Our results indicate that the most stable acetonitrile cation structure is CH2CNH+ and that hydrogenation can occur successively without isomerization steps until its complete saturation. Moreover, the stability of distinct cluster families formed from the interaction of acetonitrile with small fragments, such as CHn+, C2Hn+, and CHnCNH+, is discussed in terms of their respective binding energies. Some of these molecular clusters are stabilized by hydrogen bonds, leading to species whose infrared features are characterized by a strong redshift of the N–H stretching mode. Finally, the rotational spectra of CH3CN and protonated acetonitrile, CH3CNH+, were simulated using distinct computational protocols based on DFT, MP2, and CCSD(T) considering centrifugal distortion, vibrational–rotational coupling, and vibrational anharmonicity corrections. By adopting an empirical scaling procedure for calculating spectroscopic parameters, we were able to estimate the rotational frequencies of CH3CNH+ with an expected average error below 1 MHz for J values up to 10.

Item Type: Article
DOI/Identification number: 10.1021/acs.jpca.0c03529
Divisions: Divisions > Division of Natural Sciences > Chemistry and Forensics
Funders: National Council for Scientific and Technological Development (https://ror.org/03swz6y49)
Coordenação de Aperfeicoamento de Pessoal de Nível Superior (https://ror.org/00x0ma614)
Alexander von Humboldt Foundation (https://ror.org/012kf4317)
Depositing User: Felipe Fantuzzi
Date Deposited: 30 Nov 2022 22:25 UTC
Last Modified: 04 Mar 2024 17:46 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/98558 (The current URI for this page, for reference purposes)

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