Development of a variable-temperature ion mobility/ time-of-flight mass spectrometer for separation of electronic isomers

Abstract

The construction of a liquid nitrogen-cooled ion mobility spectrometer coupled with time-of-flight mass spectrometry was implemented to demonstrate the ability to discriminate between electronic isomers. Ion mobility allows for the separation of ions based on differing cross-sections-to-charge ratio. This allows for the possible discrimination of species with same mass if the ions differ by cross-section. Time-offlight mass spectrometry was added to mass identify the separated peak for proper identification. A liquid nitrogen-cooled mobility cell was employed for a two-fold purpose. First, the low temperatures increase the peak resolution to aid in resolving the separated ions. This is necessary when isomers may have similar cross-sections. Second, low temperature shortens the mean free path and decreases the neutral buffer gas speeds allowing for more interactions between the ions and the drift gas. Kr2+ study was performed to verify instrument performance. The variable-temperature ion mobility spectrometer was utilized to separate the distonic and conventional ion forms of CH3OH, CH3F, and CH3NH2 and to discriminate between the keto and enol forms of the acetone radical cation. Density functional theory and ab initio calculations were employed to aid in proper identification of separating isomers. Monte Carlo integration tools were also developed to predict ion cross-section and resolution within a buffer gas.