Kinetic shift

{
  "id": "MLC-T-CHM-006359",
  "term": "Kinetic shift",
  "field": "Chemistry",
  "definition": "The extra energy beyond the thermochemical threshold that a precursor ion must carry before it dissociates quickly enough to be seen within the time window of a given mass spectrometry experiment. It makes the measured appearance energy higher than the true dissociation threshold. It grows with the number of vibrational degrees of freedom of the ion and with tight transition states, since both slow the unimolecular rate near threshold.",
  "subject": "Analytical Chemistry",
  "references": [
    "PAC, 2013, 85, 1515. 'Definitions of terms relating to mass spectrometry (IUPAC Recommendations 2013)' on page 1559 (https://doi.org/10.1351/PAC-REC-06-04-06)"
  ],
  "url": "https://mlchart.com/terminology/chemistry/kinetic-shift/"
}