Non-thermal internal energy distribution of ions observed in an electrospray source interfaced with a sector mass spectrometer

David Rondeau, Nicolas Galland, Emilie Laure Zins, Claude Pepe, L. Drahos, K. Vékey

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The internal energy distribution P(Eint) of ions emitted in an electrospray (ESI) source interfaced with a sector mass spectrometer is evaluated by using the experimental survival yield (SY) method including the kinetic shift. This method is based on the relationship between the degree of fragmentation of an ion and its amount of internal energy and uses benzylpyridinium cations due to their simple fragmentation scheme. Quantum chemical calculations are performed, namely at G3(MP2)//B3LYP and QCISD/MP2 levels of theory. The results show that the internal energy distribution of the ions emitted in the ESI source interfaced with a sector analyzer is very narrow. The MassKinetics software is used to confirm these observations. The P(E int) is the parameter that allows to fit the experimental SY of each substituted benzylpyridinium cation with theoretical mass spectra generated by the MassKinetics software. The resulting internal energy distributions are similar to the ones obtained with the experimental SY method. This indicates that in the present experimental conditions, P(Eint) cannot be compared with a 'thermal-like' Boltzmann distribution. In addition, it appears that with the sector analyzer, increasing the collision energy in the first pumping stage of the ESI source does not correspond to a warm-up of the produced ions.

Original languageEnglish
Pages (from-to)100-111
Number of pages12
JournalJournal of Mass Spectrometry
Volume46
Issue number2
DOIs
Publication statusPublished - Feb 2011

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Mass spectrometers
internal energy
mass spectrometers
energy distribution
sectors
Ions
Cations
analyzers
fragmentation
ions
Software
Positive ions
computer programs
cations
Boltzmann distribution
mass spectra
pumping
Hot Temperature
Kinetics
collisions

Keywords

  • electrospray ionization
  • internal energy
  • RRKM
  • sector mass spectrometer
  • thermometer ions

ASJC Scopus subject areas

  • Spectroscopy

Cite this

Non-thermal internal energy distribution of ions observed in an electrospray source interfaced with a sector mass spectrometer. / Rondeau, David; Galland, Nicolas; Zins, Emilie Laure; Pepe, Claude; Drahos, L.; Vékey, K.

In: Journal of Mass Spectrometry, Vol. 46, No. 2, 02.2011, p. 100-111.

Research output: Contribution to journalArticle

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