Assigning Structures to Ions in Mass Spectrometry describes the tools currently available for determining gas-phase ion structures. It surveys current experimental methods for ion production and separation as well as those designed to reveal qualitative and quantitative aspects of gas-phase ions. It also examines how and when to apply computational chemistry and theoretical calculations. Selected case studies illustrate specific challenges associated with ion structure assignment and thermochemical problems. Bringing together key results collected over the past four decades, the book contains the data for describing or identifying ions containing C alone and C with H, O, N, S, P, halogens, and small organic cations.

John L. Holmes, Christiane Aubry, Paul M. Mayer

PART I: THEORY AND METHODS Tools for Identifying the Structure of Gas-Phase Ions Introduction How Ions Are Generated and Separated for Analysis Thermochemistry-Its Role in Assigning Ion Structures Experiments with Mass-Selected Ions Reactivity of Ions; Another Tool for Ion Structure Determination Use of Computational Chemistry in Ion Structure Determination What and What Not to Expect from Gas-Phase Ions Introduction Identification of a New Class of Ions: Distonic Ions The McLafferty Rearrangement: A Concerted or Stepwise Process? Peptide Ion Fragmentation: The Structure of b-Type Ions The Need for Computational Chemistry: The Methylacetate Ion Story A Problem with Neutral Thermochemistry: DfH(CH3CH2OOH) Revisited Some Advice When Assigning Structures to Gas-Phase Ions References to Part 1 PART II: IONS CONTAINING C AND POLYATOMIC IONS CONTAINING ONE TO THREE C ATOMS Ion Structures Introduction Thermochemical Data Ions Containing Only Carbon Atoms Isomers/Identification References Ions Containing One Carbon Atom References Ions Containing Three Carbon Atoms Index of C1 to C3 Ion Formulae Index