Thermochemical determinations by the kinetic method

Graham Cooks (Corresponding Author), Jeffrey Patrick, Tapio Kotiaho, Scott McLuckey

Research output: Contribution to journalReview ArticleScientificpeer-review

507 Citations (Scopus)

Abstract

Under appropriate conditions, the kinetics of the dissociation of molecular cluster ions can yield relative, but quantitative, thermochemical information on the constituent species. Cluster ions bound via protons, electrons, or other atomic or polyatomic anions or cations can be isolated and their dissociations followed in a tandem mass spectrometry experiment. The isolated, internally excited, proton-bound dimers of organic molecules dissociate competitively to yield the individual protonated monomers to a relative extent which is quantitatively related to the difference in proton affinities of the two monomers. This review (i) describes the origins of the kinetic method; (ii) explores its theoretical basis and the validity of the approximations that underlie it: (iii) surveys the use of the kinetic method to study gas-phase acidity and basicity, and when possible compares the data it yields to those derived from conventional ion/molecule reaction studies; (iv) summarizes emerging applications of the method to measurements on biological compounds, including amino acids, peptides, and nucleosides; (v) describes applications of the kinetic method to the measurement of other thermochemical properties, including electron, metal ion, and halogen cation affinities; (vi) notes some new areas of application of the kinetic method, including its use to investigate steric, electronic, and structural effects in cluster ions, and to measure proton affinities of free radicals; and (vii) covers recent experimental studies that corroborate and refine the underlying theoretical treatment of the method. Future applications, including the use of molecular clusters as thermometer ions and the estimation of thermochemical properties of short-lived or otherwise inaccessible chemical entities, are also suggested.
Original languageEnglish
Pages (from-to)287-339
Number of pages52
JournalMass Spectrometry Reviews
Volume13
Issue number4
DOIs
Publication statusPublished - 1994
MoE publication typeA2 Review article in a scientific journal

Fingerprint

Ions
Protons
Kinetics
kinetics
thermochemical properties
affinity
molecular clusters
protons
ions
Cations
monomers
Monomers
dissociation
cations
nucleosides
Molecules
Halogens
Electrons
Thermometers
thermometers

Cite this

Cooks, G., Patrick, J., Kotiaho, T., & McLuckey, S. (1994). Thermochemical determinations by the kinetic method. Mass Spectrometry Reviews, 13(4), 287-339. https://doi.org/10.1002/mas.1280130402
Cooks, Graham ; Patrick, Jeffrey ; Kotiaho, Tapio ; McLuckey, Scott. / Thermochemical determinations by the kinetic method. In: Mass Spectrometry Reviews. 1994 ; Vol. 13, No. 4. pp. 287-339.
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Cooks, G, Patrick, J, Kotiaho, T & McLuckey, S 1994, 'Thermochemical determinations by the kinetic method', Mass Spectrometry Reviews, vol. 13, no. 4, pp. 287-339. https://doi.org/10.1002/mas.1280130402

Thermochemical determinations by the kinetic method. / Cooks, Graham (Corresponding Author); Patrick, Jeffrey; Kotiaho, Tapio; McLuckey, Scott.

In: Mass Spectrometry Reviews, Vol. 13, No. 4, 1994, p. 287-339.

Research output: Contribution to journalReview ArticleScientificpeer-review

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T1 - Thermochemical determinations by the kinetic method

AU - Cooks, Graham

AU - Patrick, Jeffrey

AU - Kotiaho, Tapio

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N2 - Under appropriate conditions, the kinetics of the dissociation of molecular cluster ions can yield relative, but quantitative, thermochemical information on the constituent species. Cluster ions bound via protons, electrons, or other atomic or polyatomic anions or cations can be isolated and their dissociations followed in a tandem mass spectrometry experiment. The isolated, internally excited, proton-bound dimers of organic molecules dissociate competitively to yield the individual protonated monomers to a relative extent which is quantitatively related to the difference in proton affinities of the two monomers. This review (i) describes the origins of the kinetic method; (ii) explores its theoretical basis and the validity of the approximations that underlie it: (iii) surveys the use of the kinetic method to study gas-phase acidity and basicity, and when possible compares the data it yields to those derived from conventional ion/molecule reaction studies; (iv) summarizes emerging applications of the method to measurements on biological compounds, including amino acids, peptides, and nucleosides; (v) describes applications of the kinetic method to the measurement of other thermochemical properties, including electron, metal ion, and halogen cation affinities; (vi) notes some new areas of application of the kinetic method, including its use to investigate steric, electronic, and structural effects in cluster ions, and to measure proton affinities of free radicals; and (vii) covers recent experimental studies that corroborate and refine the underlying theoretical treatment of the method. Future applications, including the use of molecular clusters as thermometer ions and the estimation of thermochemical properties of short-lived or otherwise inaccessible chemical entities, are also suggested.

AB - Under appropriate conditions, the kinetics of the dissociation of molecular cluster ions can yield relative, but quantitative, thermochemical information on the constituent species. Cluster ions bound via protons, electrons, or other atomic or polyatomic anions or cations can be isolated and their dissociations followed in a tandem mass spectrometry experiment. The isolated, internally excited, proton-bound dimers of organic molecules dissociate competitively to yield the individual protonated monomers to a relative extent which is quantitatively related to the difference in proton affinities of the two monomers. This review (i) describes the origins of the kinetic method; (ii) explores its theoretical basis and the validity of the approximations that underlie it: (iii) surveys the use of the kinetic method to study gas-phase acidity and basicity, and when possible compares the data it yields to those derived from conventional ion/molecule reaction studies; (iv) summarizes emerging applications of the method to measurements on biological compounds, including amino acids, peptides, and nucleosides; (v) describes applications of the kinetic method to the measurement of other thermochemical properties, including electron, metal ion, and halogen cation affinities; (vi) notes some new areas of application of the kinetic method, including its use to investigate steric, electronic, and structural effects in cluster ions, and to measure proton affinities of free radicals; and (vii) covers recent experimental studies that corroborate and refine the underlying theoretical treatment of the method. Future applications, including the use of molecular clusters as thermometer ions and the estimation of thermochemical properties of short-lived or otherwise inaccessible chemical entities, are also suggested.

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