The dissociation of highly vibrationally excited molecular ions resulting from single infrared photon absorption has been studied. The wavelength dependence of the absorption/dissociation process has been measured, and the photofragments identified. Measurements were also made of the dissociative lifetime following absorption and the photofragment kinetic energy distributions. These measurements show that a strong correlation exists between this single photon dissociation process and the final step of multiphoton dissociation. Based on these results, the dissociation dynamics appear to follow a single statistical mechanism. (Author).

Collision induced dissociation and infrared multiphoton dissociation of ions formed in di- and triethylamine, di- and tri-n-propylamine, and diisopropylamine were investigated by Fourier transform ion cyclotron resonance mass spectrometry. Molecular ions of all amines except di-n-propylamine produced similar fragment ions when subjected to either dissociation technique. The initial fragmentation involved C(alpha)-C(beta) bond cleavage, loss of an alkyl radical, and formation of an immonium ion. Subsequent fragmentations of the immonium ions produced by both dissociation mechanisms involved McLafferty type rearrangements and loss of alkenes. The molecular ion of di-n-propylamine fragmented by a different mechanism when subjected to infrared irradiation. Protonated molecules of di- and tri-n-propylamine yielded C3H6 and an ammonium ion upon infrared multiphoton dissociation, while protonated molecules of the other amines did not dissociate using this technique. Collision induced dissociation, on the other hand, produced fragmentation for all protonated molecules. Explanation of the different fragmentations observed for the two dissociation techniques is given in terms of a mechanism involving a tight transition state for protonated di- and tri-n-propylamine dissociation. Keywords: Infrared Multiphoton Dissociation; Collision Induced Dissociation; Alkylamines; Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

Breaking down large biomolecules into fragments in a controlled manner is key to modern biomolecular mass spectrometry. This book is a high-level introduction, as well as a reference work for experienced users, to ECD, ETD, EDD, NETD, UVPD, SID, and other advanced fragmentation methods. It provides a comprehensive overview of their history, mechanisms, instrumentation, and key applications. With contributions from leading experts, this book will act as an authoritative guide to these methods. Aimed at postgraduate and professional researchers, mainly in academia, but also in industry, it can be used as supplementary reading for advanced students on mass spectrometry or analytical (bio)chemistry courses.

Provides comprehensive coverage of laser-induced ionization processes for mass spectrometry analysis Drawing on the expertise of the leading academic and industrial research groups involved in the development of photoionization methods for mass spectrometry, this reference for analytical scientists covers both the theory and current applications of photo-induced ionization processes. It places widely used techniques such as MALDI side by side with more specialist approaches such as REMPI and RIMS, and discusses leading edge developments in ultrashort laser pulse desorption, to give readers a complete picture of the state of the technology. Photoionization and Photo-Induced Processes in Mass Spectrometry: Fundamentals and Applications starts with a complete overview of the fundamentals of the technique, covering the basics of the gas phase ionization as well as those of laser desorption and ablation, pulse photoionization, and single particle ionization. Numerous application examples from different analytical fields are described that showcase the power and the wide scope of photo ionization in mass spectrometry. -The first general reference book on photoionization techniques for mass spectrometry -Examines technologies and applications of gas phase resonance-enhanced multiphoton ionization mass spectrometry (REMPI-MS) and gas phase resonance ionization mass spectrometry (RIMS) -Provides complete coverage of popular techniques like MALDI -Discusses the current and potential applications of each technology, focusing on process and environmental analysis Photoionization and Photo-Induced Processes in Mass Spectrometry: Fundamentals and Applications is an excellent book for spectroscopists, analytical chemists, photochemists, physical chemists, and laser specialists.

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