Mass spectral fragmentation pathways in RDX and HMX. A mass analyzed ion kinetic energy spectrometric/collisional induced dissociation study

Abstract

A collisional induced dissociation study of 1,3,5‐trinitro‐1,3,5 triazacyclohexane (RDX) and 1,3,5,7‐tetranitro‐1,3,5,7‐tetrazacyclooctane (HMX) was carried out using mass analyzed kinetic energy spectrometry. High resolution mass spectra and mass analyzed ion kinetic energy/collisional induced dissociation spectra of RDX and HMX were recorded in the electron impact, chemical ionization and negative ion chemical ionization modes. Fragmentation pathways of the compounds investigated were determined in all three modes of ionization. It was found that a major part of the fragment ions in RDX and HMX originate from formation of the aduct ions [M+NO]⁺ and [M+NO₂]⁺ in electron impact and chemical ionization, and from [M+NO]⁻ and [M+NO₂]⁻ in negative chemical ionization, followed by dissociation.