On the rapidity of ion–molecule reactions

Talrose, V.L.; Vinogradov, P. S.; Larin, I. K.

doi:10.1016/b978-0-12-120801-1.50014-4

Cited by 29 publications

(19 citation statements)

References 49 publications

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“…The assumption of no reverse activation barriers is often a reasonable one for ion±molecule reactions due to the strong long-range ion-induced dipole potential (Talrose, Vinogradov & Larin, 1979). Further, noncovalent bonds are cleaved heterolytically (i.e., the electrons making up the bond both accompany a single fragment), and it has been shown that the electronic surfaces for such dissociations should have no barriers (Armentrout & Simons, 1992), although curve crossings with surfaces of different spin could alter this conclusion.…”

Section: Experimental Methodsmentioning

confidence: 99%

Noncovalent metal-ligand bond energies as studied by threshold collision-induced dissociation

Rodgers

Armentrout

2000

Mass Spectrom. Rev.

332

306

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This review focuses on noncovalent metal ion–ligand complexes and measurements of the bond energies of such species. The method utilized in this work is threshold collision‐induced dissociation (CID), as achieved using a guided ion beam tandem mass spectrometer. Accurate determination of bond energies requires attention to many details of the experiments and data analysis. These details are discussed thoroughly and compared to other methods. A comprehensive listing of metal–ligand bond dissociation energies determined by threshold CID is provided. This list includes a variety of metals (alkalis, magnesium, aluminum, and first and second row transition metals), many different types of ligands, and variations in the number of ligands. The trends in these values are discussed, and we elucidate the importance of ion–dipole and ion–induced dipole interactions, chelation, different conformers and tautomers, steric interactions, solvation phenomena, and electronic effects such as hybridization and promotion. © 2000 John Wiley & Sons, Inc., Mass Spec Rev 19: 215–247, 2000

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Section: Experimental Methodsmentioning

confidence: 99%

Noncovalent metal-ligand bond energies as studied by threshold collision-induced dissociation

Rodgers

Armentrout

2000

Mass Spectrom. Rev.

332

306

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“…For both types of systems, the equivalence of thresholds with such thermodynamic properties relies on the assumption that there are no activation barriers in excess of the endothermicity of the reactions. In many respects, this is a key reason to perform such studies with ions because the intrinsic long-range ion induced dipole potentials involved help overcome the types of small barriers commonly observed for neutral systems [2,3]. Certainly, this assumption need not apply in all systems studied; for instance, restrictions resulting from spin or orbital angular momentum conservation can occur [3,4].…”

mentioning

confidence: 99%

“…For example, we have used reactions 1 to measure the binding energies of ionic transition metal atoms and clusters to ligands such as H, OH x (x ϭ 0 -1), NH x (x ϭ 0 -2), C y H x (y ϭ 1-4, x ϭ 0 -2y ϩ 1), SH x (x ϭ 0 -1), and SiH x (x ϭ 0 -3). CID studies have encompassed an even broader range of systems including metals throughout the periodic table and ligands such as rare gas atoms, H 2 , N 2 , CO, NO, CO 2 , H 2 O, NH 3 , CH 4 , larger alkanes, C 2 H 4 , larger alkenes, alkynes, alcohols, amines, ethers, aldehydes, ketones, crown ethers, benzene, substituted benzenes, azoles, azines, amino acids, and nucleic acids. In our laboratory, studies have included over 50 different elemental ions.…”

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confidence: 99%

Mass spectrometry—Not just a structural tool: The use of guided ion beam tandem mass spectrometry to determine thermochemistry

Armentrout

2002

J. Am. Soc. Mass Spectrom.

173

180

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Guided ion beam tandem mass spectrometry has proved to be a robust tool for the measurement of thermodynamic information. Over the past twenty years, we have elucidated a number of factors necessary to make such thermochemistry accurate. Careful attention must be paid to the reduction of the raw data, ion intensities versus laboratory ion energies, to a more useful form, reaction cross sections versus relative kinetic energy. Analysis of the kinetic energy dependence of cross sections for endothermic reactions can then reveal thermodynamic data for both bimolecular and collision-induced dissociation (CID) processes. Such analyses need to include consideration of the explicit kinetic and internal energy distributions of the reactants, the effects of multiple collisions, the identity of the collision partner in CID processes, the kinetics of the reaction being studied, and competition between parallel reactions. This work provides examples illustrating the need to consider this multitude of effects along with details of the procedures developed in our group for handling each of them. ( W hen does a mass spectrometer become an ion beam instrument? Is this defined by the instrument, by whether the operator is an analytical or physical chemist, or by the experiments done? All mass spectrometers utilize ion beams, but the unspoken definition of an ion beam instrument is an apparatus that can be used to make quantitative physical measurements. In this regard, the capabilities of the instrumentation and the intent and training of the operator are all important factors. Whereas a mass spectrometer is often used as an identification tool through the use of mass spectral patterns, by taking advantage of the ability to easily change the kinetic energy of ions, it can also be a powerful instrument for the determination of thermodynamic data.In this article, I lay down some of the founding principles behind our use of tandem mass spectrometry, and in particular, so-called guided ion beam mass spectrometry to elucidate thermochemical information. This is achieved primarily by examining the kinetic energy dependence of endothermic ion-molecule reactions and determining their energy thresholds.Although many types of instruments have been used to perform such measurements, the link between such studies and guided ion beam techniques is a strong one. Indeed, the NIST Webbook [1] states in its section on Determinations of Reaction Endothermicity that "more commonly a so-called guided-beam apparatus is utilized for such determinations." Considering that there are only about a dozen such laboratories worldwide, this is a testament to the ability of this particular kind of apparatus to provide a plethora of high quality information. However, such information requires attention to myriad details, which are outlined in this article.Two fundamental types of reactions can be used to acquire thermodynamic information: Bimolecular exchange reactions, process 1, and collision-induced dissociation (CID), process 2.Reactions 1 can be either ex...

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“…Perhaps the greatest advantage of gas-phase ion-molecule or ion-ion reactions is that these reactions often have little or no activation barrier (Talrose, Vinogradov, & Larin, 1979). The absence of a solvent in the gas phase eliminates much of the activation energy normally required for condensed-phase reactions and increases reaction rates by minimizing or eliminating the potential-energy barrier of desolvation.…”

Section: Plasma Ionization Sources For Unique Chemical Transformationsmentioning

confidence: 99%

“…One way to increase the signal of analyte ions, which does not involve a change in the reaction pathway, is to increase the abundance of reagent ions to kinetically drive ionization reactions forward (Franklin, 1972; Talrose, Vinogradov, & Larin, 1979). For a given residence time of an analyte species within the ionization source, a higher abundance of reagent ions leads to more analyte ions available for mass analysis and, thus, better sensitivity and LODs.…”

Section: Plasma Ionization For Organic Msmentioning

confidence: 99%

Modern Plasma‐based Desorption/Ionization: From Atoms and Molecules to Chemical Synthesis

Molnar

Shelley

2020

Mass Spectrometry Reviews

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Since the first mass spectrometry (MS) experiments were conducted by Thomson and Aston, plasmas have been used as ionization sources. Historically, plasma ion sources were used for these experiments because they were one of the few known sources of gasphase ions at the time and they were relatively simple to setup and operate. Since then, developments in plasma ionization have continued to inform and motivate advances in other areas of MS. For example, plasma-desorption MS demonstrated ionization of large peptides and polymers more than 10 years before the first descriptions of electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). As a result, significant effort was placed on development of ionization approaches, mass analysis, and detection approaches for very large molecules: even before the advent of ESI and MALDI. Since then, new analytical challenges and opportunities in plasma ionization have arisen. In this review, the emerging trends in plasma-based ionization for several areas of MS will be discussed, including molecular ionization, elemental ionization, hybrid elemental and molecular ion sources, and unique chemical transformations.

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On the rapidity of ion–molecule reactions

Cited by 29 publications

References 49 publications

Noncovalent metal-ligand bond energies as studied by threshold collision-induced dissociation

Noncovalent metal-ligand bond energies as studied by threshold collision-induced dissociation

Mass spectrometry—Not just a structural tool: The use of guided ion beam tandem mass spectrometry to determine thermochemistry

Modern Plasma‐based Desorption/Ionization: From Atoms and Molecules to Chemical Synthesis

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