This work applies the technique of mapping ion detection using a reflectron mass spectrometer against flight-time and reflection voltage to elucidate the complex metastable fragmentation pattern of the biomolecular ion 3-aminophenol + (3-AP + , C 6 H 7 NO + ). Multi-photon ionization experiments revealed the excited ion's fragmentation routes for the first time and comparisons with calculated flight-times enabled 18 different μs-timescale dissociations to be assigned. These included the rare observation of a double hydrogen loss channel from a fragment ion. DFT calculations provided further insights into the most prominent apparent fragmentation sequence: 3-AP + (m/z 109) → HCO + C 5 H 6 N + (m/z 80) → CNH + C 4 H 5 + (m/z 53) → C 2 H 2 + C 2 H 3 + (m/z 27).
- DFT calculations
- Double hydrogen loss
- Metastable fragmentation
- Reflectron time-of-flight mass spectrometry
- Sequential fragmentation