Ion Dissociation Kinetics in Mass Spectrometry

Unimolecular rate constant; microcanonical rate constant; canonical rate constant; kinetic isotope effects; reaction mechanisms; non-adiabatic processes; tunneling; isolated state decay; transition state theory; RRKM theory; kinetic energy release

Abstract :

[en] The variation of fragmentation rate constants as a function of the parent ion internal energy, or, alternatively, as a function of temperature, is crucial information to unravel the dissociation mechanisms of molecular ions. This contribution provides the reader first with basic information on the statistical theories used to model unimolecular rate constants. Various experimental methods to measure such rate constants in the 102 to 1010 s^(-1) range are then discussed. Kinetic isotope effects are also briefly dealt with. How reaction mechanisms can be inferred from kinetic data is handled in an extensive section where selected examples from the recent literature are discussed.

Research center :

Department of Chemistry, University of Liège

Disciplines :

Chemistry

Author, co-author :

Leyh, Bernard ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire

Language :

English

Title :

Ion Dissociation Kinetics in Mass Spectrometry

Alternative titles :

[fr] Cinétique des dissociations ioniques en spectrométrie de masse

Publication date :

2013

Main work title :

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

Editor :

Reedijk, J.

Publisher :

Elsevier, Waltham, United States - Massachusetts

Peer reviewed :

Peer reviewed

Additional URL :

http://www.sciencedirect.com/science/referenceworks/9780124095472

Funders :

ULiège - Université de Liège [BE]

Available on ORBi :

since 21 October 2013

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Bibliography

Ferrier, B., Boulanger, A.M., Holland, D.M.P., Shaw, D.A., Mayer, P.M., Nitro-Nitrite Isomerization and Transition State Switching in the Dissociation of Ionized Nitromethane: A Threshold Photoelectron-Photoion Coincidence Spectroscopy Study (2009) Eur. J. Mass Spectrom., 15, pp. 157-166
Moon, J.H., Yoon, S.H., Bae, Y.J., Kim, M.S., Dissociation Kinetics of Singly Protonated Leucine Enkephalin Investigated by Time-Resolved Photodissociation Tandem Mass Spectrometry (2010) J. Am. Soc. Mass Spectrom., 21, pp. 1151-1158
Baer, T., Tsai, B.P., Smith, D., Murray, P.T., Absolute Unimolecular Decay Rates of Energy-Selected Metastable Halobenzene Ions (1976) J. Chem. Phys., 64, pp. 2460-2465
Baer, T., Kury, R., Random Energy Flow in the Dissociation of Energy-Selected Bromobenzene and Bromobenzene-d5 Ions (1982) Chem. Phys. Lett, 92, pp. 659-662
Rosenstock, H.M., Stockbauer, R., Parr, A.C., Photoelectron-Photoion Coincidence Study of the Bromobenzene Ion (1980) J. Chem. Phys., 73, pp. 773-777
Bodi, A., Johnson, M., Gerber, T., Gengeliczki, Z., Sztáray, B., Baer, T., Imaging Photoelectron Photoion Coincidence Spectroscopy with Velocity Focusing Electron Optics (2009) Rev. Sci. Instrum., 80. , 1-7
Stevens, W., Sztáray, B., Shuman, N., Baer, T., Troe, J., Specific Rate Constants k(E) of the Dissociation of the Halobenzene Ions: Analysis by Statistical Unimolecular Rate Theories (2009) J. Phys. Chem. A, 113, pp. 573-582
Pratt, S.T., Chupka, W.A., Photoionization Study of the Kinetics of Unimolecular Decomposition of Halobenzene Ions (1981) Chem. Phys., 62, pp. 153-163
Brand, W.A., Stockloev, J., Walther, H.-J., Conversion of Field Ionization Kinetics Data to Unimolecular Rate Constant Functions. A Simple Numerical Approach. Int. J. Mass Spectrom (1984) Ion Processes, 59, pp. 1-20
Lim, S.-H., Choe, J.C., Kim, M.S., C6H5Br+• → C6H5+ + Br• Occurs Via Orbiting Transition State (1998) J. Phys. Chem. A, 102, pp. 7375-7381
Malinovich, Y., Arakawa, R., Haase, G., Lifshitz, C., Time-Dependent Mass Spectra and Breakdown Graphs. 6. Slow Unimolecular Dissociation of Bromobenzene Ions at Near Threshold Energies (1985) J. Phys. Chem., 89, pp. 2253-2260
Rosenstock, H.M., Stockbauer, R., Parr, A.C., Photoelectron-Photoion Coincidence Study of Benzonitrile (1980) Journal de Chimie Physique, 77, pp. 745-750
Lifshitz, C., Tropylium Ion Formation from Toluene: Solution of an Old Problem in Organic Mass Spectrometry (1994) Acc. Chem. Res, 27, pp. 138-144
Fati, D., Lorquet, A.J., Locht, R., Lorquet, J.C., Leyh, B., Kinetic Energy Release Distributions for Tropylium and Benzylium Ion Formation from the Toluene Cation (2004) J. Phys. Chem. A, 108, pp. 9777-9786
Longevialle, P., Ion-Neutral Complexes in the Unimolecular Reactivity of Organic Cations in the Gas Phase (1992) Mass Spectrom. Rev., 11, pp. 157-192
Booze, J.A., Baer, T., Dissociation Dynamics of Energy-Selected Propanol Ions from a σ-Type Ion Structure (1992) J. Phys. Chem., 96, pp. 5715-5719
Locht, R., Dehareng, D., Hottmann, K., Jochims, H.W., Baumgärtel, H., Leyh, B., The Photoionization Dynamics of Methyl Iodide (CH3I): A Joint Photoelectron and Mass Spectrometric Investigation (2010) J. Phys. B., 43, p. 105101
Aschi, M., Harvey, J.N., Schalley, C.A., Schröder, D., Schwarz, H., Reappraisal of the Spin-Forbidden Unimolecular Decay of the Methoxy Cation (1998) Chem. Comm., pp. 531-532
Bodi, A., Brannock, M.D., Sztáray, B., Baer, T., Tunneling in H loss from Energy Selected Ethanol Ions (2012) Phys. Chem. Chem. Phys., 14, pp. 16047-16054
Gridelet, E., Dehareng, D., Locht, R., Lorquet, A.J., Lorquet, J.C., Leyh, B., Ground and Excited State Dissociation Dynamics of Ionized 1,1-Difluoroethylene (2005) J. Phys. Chem. A, 109, pp. 8225-8235
Baer, T., Hase, W.L., Unimolecular Reaction Dynamics (1996) Theory and Experiments, , Oxford University Press, Oxford
Drahos, L., Vékey, K., MassKinetics: A Theoretical Model of Mass Spectra Incorporating Physical Processes, Reaction Kinetics and Mathematical Descriptions (2001) J. Mass Spectrom., 36, pp. 237-263
Dunbar, R.C., BIRD (Blackbody infrared radiative dissociation): Evolution, Principles and Applications (2004) Mass Spectrom. Rev., 23, pp. 127-158
Forst, W., Unimolecular Reactions (2003) A Concise Introduction, , Cambridge University Press, Cambridge
Gilbert, R.G., Smith, S.C., (1990) Theory of Unimolecular and Recombination Reactions, , Blackwell Scientific Publications, Oxford
Leyh, B., Lorquet, J.C., Kinetic Energy Release Distributions in Mass Spectrometry (2003) The Encyclopedia of Mass Spectrometry, 1, pp. 17-32. , Elsevier, Oxford, Chapter 1, M.L. Gross, R. Caprioli, P.B. Armentrout (Eds.)
Lifshitz, C., Some Recent Aspects of Unimolecular Gas Phase Ion Chemistry (2001) Chem. Soc. Rev., 30, pp. 186-192
Lorquet, J.C., Leyh, B., Statistical Theories in Mass Spectrometry (2003) The Encyclopedia of Mass Spectrometry, 1, pp. 8-17. , Elsevier, Oxford, Chapter 1, M.L. Gross, R. Caprioli, P.B. Armentrout (Eds.)
Lorquet, J.C., Leyh, B., Non-Adiabatic Reactions (2003) The Encyclopedia of Mass Spectrometry, 1, pp. 33-40. , Elsevier, Oxford, Chapter 1, M.L. Gross, R. Caprioli, P.B. Armentrout (Eds.)
Steinfeld, J.I., Francisco, J.S., Hase, W.L., (1999) Chemical Kinetics and Dynamics, , Prentice Hall, Upper Saddle River
Sztáray, B., Bodi, A., Baer, T., Modeling Unimolecular Reactions in Photoelectron Photoion Coincidence Experiments (2010) J. Mass Spectrom., 45, pp. 1233-1245