Collision-induced dissociation spectroscopy

Time-of-flight mass spectrometers have been used as detectors in a wider variety of experiments tlian any other mass spectrometer. This is especially true of spectroscopic applications, many of which are discussed in this encyclopedia. Unlike the other instruments described in this chapter, the TOP mass spectrometer is usually used for one purpose, to acquire the mass spectrum of a compound. They caimot generally be used for the kinds of ion-molecule chemistry discussed in this chapter, or structural characterization experiments such as collision-induced dissociation. Plowever, they are easily used as detectors for spectroscopic applications such as multi-photoionization (for the spectroscopy of molecular excited states) [38], zero kinetic energy electron spectroscopy [39] (ZEKE, for the precise measurement of ionization energies) and comcidence measurements (such as photoelectron-photoion coincidence spectroscopy [40] for the measurement of ion fragmentation breakdown diagrams). 

The apparatus and techniques of ion cyclotron resonance spectroscopy have been described in detail elsewhere. Ions are formed, either by electron impact from a volatile precursor, or by laser evaporation and ionization of a solid metal target (14), and allowed to interact with neutral reactants. Freiser and co-workers have refined this experimental methodology with the use of elegant collision induced dissociation experiments for reactant preparation and the selective introduction of neutral reactants using pulsed gas valves (15). Irradiation of the ions with either lasers or conventional light sources during selected portions of the trapped ion cycle makes it possible to study ion photochemical processes... 

Key words clusters, ion mobility spectrometry, photoelectron spectroscopy, collision-induced dissociation, molecular structure optimization... 

Gas-phase acid-base studies are usually performed by using one of the following techniques high-pressure mass spectrometry (HPMS), chemical ionization mass spectroscopy (CIMS) with mass-analysed ion kinetic energy spectroscopy/collision induced dissociation (MIKES/CID), flowing afterglow (FA) or ion cyclotron resonance (ICR) spectrometry. For a brief description of all methods, Reference 8 should be consulted. 

In addition to UV/visible flash photolysis and TRIR spectroscopy, other techniques have been used for the detection of transition metal-noble gas interactions in the gas phase. The interaction of noble gases with transition metal ions has been studied in detail. A series of cationic dimeric species, ML" " (M = V, Cr, Fe, Co, Ni L = Ar, Kr, or Xe), have been detected by mass-spectroscopic methods (55-58). It should be noted that noble gas cations L+ are isoelectronic with halogen atoms, therefore, this series of complexes is not entirely unexpected. The bond dissociation energies of these unstable complexes (Table IV) were determined either from the observed diabatic dissociation thresholds obtained from their visible photodissociation spectra or from the threshold energy for collision-induced dissociation. The bond energies are found to increase linearly with the polarizability of the noble gas. 

The product of the collision-induced dissociative chemisorption event is identified by high resolution electron energy loss spectroscopy. Fig. 9a shows the vibrational spectrum of a monolayer of methane at 46 K before bombardment with Ar. The vibrational frequencies are unperturbed from the gas phase values within the resolution of this technique ( 20 cm-1). The loss observed at 1305 cm" is assigned to the V4 mode, the loss at 1550 cm- to the >2 mode and the losses at 2895 cm 1 and 3015 cm- to the vi and V3 modes, respectively. Fig. 9b shows the vibrational spectrum after exposure of the methane monolayer at 46 K to a beam of Ar atoms with a translational energy of 36 kcal/mole. This spectrum has been assigned previously to an adsorbed methyl radical. 

Associated methods of relevance in gas-phase ion chemistry comprise ion activation/dissociation (McLuckey and Mentinova, 2011), where collision-induced dissociation (CID) stands out due to its generalized use, and ion spectroscopy (Baer and Dunbar, 2010 Polfer, 2011 Roithova, 2012) again, key descriptions of these methods also appear in the first volume of The Encyclopedia of Mass Spectrometry (Armentrout et al., 2003). The related aspects pertaining to ion thermochemistry will be referenced in Section 3. 

Theoretical Methods for Vibrational Spectroscopy and Collision Induced Dissociation in the Gas Phase... 

Abstract In this chapter we review recent advances in theoretical methods to understand and rationalize anharmonic vibrational spectroscopy (IR-MPD and IR-PD) and collision induced dissociations (CID) in the gas phase. We focused our attention on the application of molecular dynamics-based methods. DFT-based molecular dynamics was shown to be able to reproduce InfraRed Multi-Photon Dissociation (IR-MPD) and InfraRed Pre-Dissociation (IR-PD) action spectroscopy experiments, and help assign the vibrational bands, taking into account finite temperature, conformational dynamics, and various anharmonicities. Crucial examples of dynamical vibrational spectroscopy are given on the protonated AlanH" series (related to IR-MPD in the 800-4,0(X) cm domain), ionic clusters (related to IR-PD in the 3,000-4,(XX) cm region), and neutral peptides (related to IR-MPD in the far-lR). We give examples from simple (e.g., cationized urea) to more complex (e.g., peptides and carbohydrates) molecular systems where molecular dynamics was particularly suited to understanding CID experiments. 

The applications of quantum-based MD which we present throughout this chapter in the context of infrared vibrational spectroscopy and collision-induced dissociation rely on Bom-Oppenheimer MD simulations, briefly outlined below. Within Bom-Oppenheimer MD, the static (time-independent) Schrodinger equation is solved at each step of the dynamics, i.e., for each configuratirai of the nuclei ... 

We now conclude this chapter by a discussirai of what we think are the challenges to be tackled by theoreticians in the years to come in the two domains of gas phase spectroscopy and collision-induced dissociation modeling, but also some challenges that, we theoreticians, would like to suggest to the experimentalists to strengthen our knowledge of structural and dynamical information of gas phase molecular assemblies. 

Atkins CG, Banu L, Rowsell M, Blagojevic V, Bohme DK, Pridgen TD (2009) Structure of [Pb(Gly-H)](-i-) and the monosolvated water and methanol solvated species by infrared multiple-photon dissociation spectroscopy, energy-resolved collision-induced dissociation, and electronic structure calculations. J Phys Chem B 113 14457-14464... 

The use of gas-phase biomolecule spectroscopy for structural characterization rehes strongly on the interplay between experiment and theory. Structural properties can usually only be extracted from experimental spectra with the use of high-level quantum-chemical calculatirms. The chapter Theoretical Methods for Vibrational Spectroscopy and CoIUsirai Induced Dissociation in the Gas Phase reviews some recent advances in the theoretical methods applied to predict vibrational spectra, including molecular-dynamics-based methods to model photo-dissociation spectra and DFT-based molecular dynamics to predict spectra in the far-infrared region. The use of trajectory calculations on a semi-empirical potential is investigated as an alternative to transition-state calculations for the modeling of collision-induced dissociation of protonated peptides. 

AES Auger electron spectroscopy, atomic emission CID collision induced dissociation... 

Hulst, a. G. Kientz, C. E. Differentiation between the isomeric amino acids leucine and isoleucine using low-energy collision-induced dissociation tandem mass spectroscopy./. Mass S/7ccrrom. 1996,3/, 1188-1190. 

Mossbauer spectroscopy has not been noted in this report for some years, so it was of some interest to find that Ishiguro and co-workers have produced Sb, Fe and spectra in a detailed study on antimony-transition metal bonds in metal carbonyl derivatives of tertiary stibines. Finally, in this section, Beyer and Leary comment on energy-resolved collision-induced dissociation of Fc2(CO)/ (y = 1-9). 

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