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Application of a multivariate normal distribution methodology to the dissociation of doubly ionized molecules: The DMDS (CH 3 ‐SS‐CH 3 ) case
Author(s) -
Varas Lautaro R.,
Pontes F. C.,
Santos A. C. F.,
Coutinho L. H.,
Souza G. G. B.
Publication year - 2015
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.7257
Subject(s) - chemistry , ion , fragmentation (computing) , dissociation (chemistry) , ionic bonding , electron ionization , ionization , molecule , mass spectrometry , atomic physics , mass spectrum , collision induced dissociation , coincidence , analytical chemistry (journal) , tandem mass spectrometry , physics , chromatography , organic chemistry , computer science , operating system , medicine , alternative medicine , pathology
Rationale The ion‐ion‐coincidence mass spectroscopy technique brings useful information about the fragmentation dynamics of doubly and multiply charged ionic species. We advocate the use of a matrix‐parameter methodology in order to represent and interpret the entire ion‐ion spectra associated with the ionic dissociation of doubly charged molecules. This method makes it possible, among other things, to infer fragmentation processes and to extract information about overlapped ion‐ion coincidences. This important piece of information is difficult to obtain from other previously described methodologies. Methods A Wiley‐McLaren time‐of‐flight mass spectrometer was used to discriminate the positively charged fragment ions resulting from the sample ionization by a pulsed 800 eV electron beam. We exemplify the application of this methodology by analyzing the fragmentation and ionic dissociation of the dimethyl disulfide (DMDS) molecule as induced by fast electrons. The doubly charged dissociation was analyzed using the Multivariate Normal Distribution. Results The ion‐ion spectrum of the DMDS molecule was obtained at an incident electron energy of 800 eV and was matrix represented using the Multivariate Distribution theory. The proposed methodology allows us to distinguish information among [CH n SH n ] + /[CH 3 ] + (n = 1–3) fragment ions in the ion‐ion coincidence spectra using ion‐ion coincidence data. Using the momenta balance methodology for the inferred parameters, a secondary decay mechanism is proposed for the [CHS] + ion formation. As an additional check on the methodology, previously published data on the SiF 4 molecule was re‐analyzed with the present methodology and the results were shown to be statistically equivalent. Conclusions The use of a Multivariate Normal Distribution allows for the representation of the whole ion‐ion mass spectrum of doubly or multiply ionized molecules as a combination of parameters and the extraction of information among overlapped data. We have successfully applied this methodology to the analysis of the fragmentation of the DMDS molecule. Copyright © 2015 John Wiley & Sons, Ltd.