Evaluation of Secondary Ion Internal Energy Distribution in LSIMS

Agnello, A.; Derwa, F.; Pauw, Edwin De

doi:10.1007/978-1-4684-7926-3_14

Cited by 2 publications

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“…A survival yield measurement should theoretically represent the fraction of ions having an energy in the reaction coordinate below the E thr value whereas the rest of the internal energy is distributed in all the s oscillators of the ion. It is customary to manually add two points to the collected data, the first one at the coordinate ( SY = 0, E 0 or E thr = 0) and the second at a value SY = 1 for the highest value of E thr 23–34 . They represent the fact that all the precursor ions are fragmented for E 0 or E thr = 0 whereas they survive completely for high value for E 0 or E thr = E max .…”

Section: Introductionmentioning

confidence: 99%

“…The fragmentation scheme of a substituted benzylpyridinium cation is associated to the direct cleavage of one of the ion bonds (see Figure 1) assuming that there is no reverse critical energy along the reaction coordinate. From this assumption, E 0 can be well approximated from the heat of formation of the reaction products and the reactant 26–35 …”

Section: Introductionmentioning

confidence: 99%

“…From this assumption, E 0 can be well approximated from the heat of formation of the reaction products and the reactant. [26][27][28][29][30][31][32][33][34][35] In some works, the variation of the SY exp values is correlated with the appearance energy threshold (E thr ). 24,32,34 The latter takes into account the kinetics shift (ks) that is the excess of energy imparted in the reaction coordinate by regard to E 0 required for a dissociation reaction occurs in the time scale of experiment such as…”

mentioning

confidence: 99%

“…It is customary to manually add two points to the collected data, the first one at the coordinate (SY = 0, E 0 or E thr = 0) and the second at a value SY = 1 for the highest value of E thr . [23][24][25][26][27][28][29][30][31][32][33][34] They represent the fact that all the precursor ions are fragmented for E 0 or E thr = 0 whereas they survive completely for high value for E 0 or E thr = E max . If the curve connecting the SY exp data versus E thr values are fitted with a single symmetric sigmoid function, this one must be regarded as the normalized integral under the curve of a Gaussian function P (E thr ) such as…”

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confidence: 99%

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From electrospray ionization to cold‐spray ionization: How to evaluate the cooling effect on the gaseous ions?

Bertrand,

Rondeau,

Delhaye

et al. 2023

J Mass Spectrom

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Two methods of survival yields (SY) measurement treatment of thermometer ions whose fragmentation is activated by in‐source collision induced dissociation have been investigated for evaluating the mean internal (<Eint>) and thermal (<Etherm>) energies of gaseous ions produced by electrospray ionization and cold‐spray ionization (CSI). One of the methods is based on the use of the internal energy distributions (P (Eint)) as sigmoid derivatives connecting the experimental survival yields of different substituted benzylpyridinium cations. The <Eint> values are therefore converted in a thermal‐like parameter called vibrational temperature (Tvib) then obtained at each value of the voltage of the desolvation area. The second method is based on the modelling of ion behavior by the MassKinetics software where the value of the characteristic temperature parameter (Tchar) is used for fitting theoretical survival yields (SYtheo) with experimental data (SYexp) calculated at several activation energy. A linear correlation is evidenced between the values of internal or thermal energy and the voltage of the orifice 1 at the origin of the ion activation in the desolvation area. The extrapolation at zero voltage of the thermal‐like parameters (Tvib and Tchar) indicates that, in agreement with the literature data, the ions are relatively hot in ESI (~650 K). But the use of a CSI source lowers this temperature down to ~300 K. In addition, with cold‐spray ionization, this cooling effect is more important when methanol is used instead of acetonitrile although these two solvents have no influence on the gaseous ion temperature in electrospray ionization.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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From electrospray ionization to cold‐spray ionization: How to evaluate the cooling effect on the gaseous ions?

Bertrand,

Rondeau,

Delhaye

et al. 2023

J Mass Spectrom

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Characterization of beam-induced reactions occurring in liquid secondary ion mass spectrometry/fast-atom bombardment by tandem mass spectrometry

Agnello

Pauw

Natalis

1993

J. Am. Soc. Mass Spectrom.

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Department of General and Physical Chemistry, University of Liege, Liege, Belgium A specific beam-induced secondary reaction involving the condensation of hydroxylic matrices with some organic groups (aldehydes, ketones, etc.) accompanied by the loss of a water molecule was investigated by liquid secondary ion mass spectrometry/fast-atom bombardment (LSIMS/FAB). A mechanistic scheme and a structure of the induced product are proposed. The features of this secondary reaction were studied and the influence of the types of solutes, acidic additives, and matrices analyzed. Rather than a drawback, LSIMS/FAB mass spectrometry can take advantage of this matrix effect to infer analytical information through tandem mass spectrometry experiments. Specific neutral loss scans can be conducted to highlight beam-induced reactive molecules, even when the detection of these species is prevented in normal scan spectra by other surface-active components.

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Evaluation of Secondary Ion Internal Energy Distribution in LSIMS

Cited by 2 publications

References 3 publications

From electrospray ionization to cold‐spray ionization: How to evaluate the cooling effect on the gaseous ions?

From electrospray ionization to cold‐spray ionization: How to evaluate the cooling effect on the gaseous ions?

Characterization of beam-induced reactions occurring in liquid secondary ion mass spectrometry/fast-atom bombardment by tandem mass spectrometry

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