title: Mass resolution and mass accuracy: how much is enough?
abstract: Accurate mass measurement requires the highest possible mass resolution, to ensure that only a single elemental composition contributes to the mass spectral peak in question. Although mass resolution is conventionally defined as the closest distinguishable separation between two peaks of equal height and width, the required mass resolving power can be ∼10× higher for equal width peaks whose peak height ratio is 100 : 1. Ergo, minimum resolving power requires specification of maximum dynamic range, and is thus 10-100× higher than the conventional definition. Mass resolving power also depends on mass-to-charge ratio. Mass accuracy depends on mass spectral signal-to-noise ratio and digital resolution. Finally, the reliability of elemental composition assignment can be improved by resolution of isotopic fine structure. Thus, the answer to the question of "how much is enough mass resolving power" requires that one first specify S/N ratio, dynamic range, digital resolution, mass-to-charge ratio, and (if available) isotopic fine structure. The highest available broadband mass resolving power and mass accuracy is from Fourier transform ion cyclotron resonance mass spectrometry. Over the past five years, FT-ICR MS mass accuracy has improved by about an order of magnitude, based on higher magnetic field strength, conditional averaging of time-domain transients, better mass calibration (spectral segmentation; inclusion of a space charge term); radially dispersed excitation; phase correction to yield absorption-mode display; and new ICR cell segmentation designs.
authors.affiliation: Department of Chemistry & Biochemistry, Florida State University ; Ion Cyclotron Resonance Program, National High Magnetic Field Laboratory, Florida State University.
authors.forename: Alan
authors.initials: A
authors.lastname: G Marshall
authors.affiliation: Ion Cyclotron Resonance Program, National High Magnetic Field Laboratory, Florida State University.
authors.forename: Greg
authors.initials: G
authors.lastname: T Blakney
authors.affiliation: Department of Chemistry & Biochemistry, Florida State University.
authors.forename: Tong
authors.initials: T
authors.lastname: Chen
authors.affiliation: Ion Cyclotron Resonance Program, National High Magnetic Field Laboratory, Florida State University.
authors.forename: Nathan
authors.initials: N
authors.lastname: K Kaiser
authors.affiliation: Ion Cyclotron Resonance Program, National High Magnetic Field Laboratory, Florida State University.
authors.forename: Amy
authors.initials: A
authors.lastname: M McKenna
authors.affiliation: Department of Chemistry & Biochemistry, Florida State University ; Ion Cyclotron Resonance Program, National High Magnetic Field Laboratory, Florida State University.
authors.forename: Ryan
authors.initials: R
authors.lastname: P Rodgers
authors.affiliation: Department of Chemistry & Biochemistry, Florida State University.
authors.forename: Brian
authors.initials: B
authors.lastname: M Ruddy
authors.affiliation: Ion Cyclotron Resonance Program, National High Magnetic Field Laboratory, Florida State University.
authors.forename: Feng
authors.initials: F
authors.lastname: Xian
keywords: FTMS; Fourier transform; ion cyclotron resonance; isotopic fine structure