Document Type
Article
Original Publication Date
2020
Journal/Book/Conference Title
The Journal of Physical Chemistry A
Volume
124
Issue
37
First Page
7427
Last Page
7438
DOI of Original Publication
10.1021/acs.jpca.0c06545
Date of Submission
May 2022
Abstract
Dissociation pathways of singly- and multiply charged gas-phase nitromethane cations were investigated with strong-field laser photoionization mass spectrometry and density functional theory computations. There are multiple isomers of the singly charged nitromethane radical cation, several of which can be accessed by rearrangement of the parent CH3–NO2 structure with low energy barriers. While direct cleavage of the C–N bond from the parent nitromethane cation produces NO2+ and CH3+, rearrangement prior to dissociation accounts for fragmentation products including NO+, CH2OH+, and CH2NO+. Extensive Coulomb explosion in fragment ions observed at high laser intensity indicates that rapid dissociation of multiply charged nitromethane cations produces additional species such as CH2+, H+, and NO22+. On the basis of analysis of Coulomb explosion in the mass spectral signals and pathway calculations, sufficiently intense laser fields can remove four or more electrons from nitromethane.
Rights
2020 American Chemical Society
Is Part Of
VCU Chemistry Publications
Comments
This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Journal of Physical Chemistry A, copyright © 2020 American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acs.jpca.0c06545