Determination of rate constants for low pressure association reactions by Fourier transform-ion cyclotron resonance spectrometry

Fisher, J.J.; McMahon, T. B.

doi:10.1016/0168-1176(90)85104-a

Cited by 37 publications

(16 citation statements)

References 19 publications

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“…The probability of the formation of a stabilized complex under these conditions then depends on the competition between IR photon emission and redissociation of the metastable complex back to reactants. The strong dependence of re-dissociation rates on bond energy is the key to exploiting this process in the RA kinetics method for determining ligand/metal-ion bond energies. ,− …”

Section: Introductionmentioning

confidence: 99%

Radiative Association Kinetics and Binding Energies of Chromium Ions with Benzene and Benzene Derivatives

and

Dunbar

1997

Organometallics

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The radiative association reactions of gas-phase Cr+ with benzene and three of its methyl derivatives (toluene, p-xylene, and mesitylene) were studied in the Fourier-transform ion cyclotron resonance ion trap. Sequential formation of the monomer complexes and the sandwich dimer complexes was observed, and the kinetics were analyzed by a recently developed canonical transition-state theory approach to give estimates of the binding energies. The bond strength of Cr+−(C6H6) was assigned as 1.70 ± 0.15 eV, and the bond strengths increased slightly with increasing methyl substitution, reaching 2.0 eV for mesitylene. The bond strength for Cr+(C6H6)−(C6H6) was assigned as 2.2 ± 0.4 eV, with similar values (within large uncertainties) for the other sandwich complexes. The Cr+−(C6H6) value was in good agreement with the value from collision-induced dissociation, and a best value of 1.73 ± 0.10 eV for this bond strength is recommended.

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Section: Introductionmentioning

confidence: 99%

Radiative Association Kinetics and Binding Energies of Chromium Ions with Benzene and Benzene Derivatives

and

Dunbar

1997

Organometallics

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“…Trends of molecular size and number of normal modes have been examined on unimolecular lifetimes of the association intermediates. No apparent trends were observed to allow for the prediction of radiative stabilization lifetimes (Fisher & McMahon, 1990).…”

Section: Structures Energetics and Dynamics Of Gas Phase Ionsmentioning

confidence: 99%

Structures, energetics, and dynamics of gas phase ions studied by FTICR and HPMS

McMahon

2009

Mass Spectrometry Reviews

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Both Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and high-pressure mass spectrometry (HPMS) are very powerful tools in the field of gas phase ion chemistry. Many experimental method developments based on FTICR-MS and HPMS are summarized, including the coupling of a high-pressure external ion source to a FTICR mass spectrometer, blackbody infrared radiative dissociation (BIRD), coupling laser desorption ionization with HPMS, infrared multiple photon dissociation (IRMPD), radiative association and bimolecular routes to gas phase cluster ion formation. An abundance of thermochemical data, such as proton affinities, gas phase acidities, methyl cation affinities and metal cation affinities, have been obtained. Some of these data are the basis of the standard data listed in the NIST thermochemical databases. Ion-molecule interactions, energetics, reactivities, and structures of molecules have been extensively investigated using the methods developed based on HPMS and FTICR mass spectrometric techniques.

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“…The gas‐phase ion/molecule reactions of acetone have been studied extensively in the past 1–22. A substantial amount of the work has been focused on the formation of acetone cluster ions.…”

Section: Introductionmentioning

confidence: 99%

“…Several mass spectrometric studies have addressed the properties and structure of acetone clusters. Techniques that are central to the present work include CID (collision‐induced dissociation),1–7 IRMPD (infrared multiphoton dissociation),8 KER (kinetic energy release),9 FT‐ICR (Fourier transform ion cyclotron resonance),10–13 and PHPMS (Pulsed ionization high pressure mass spectrometry) 7, 14–19…”

Section: Introductionmentioning

confidence: 99%

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Isomerization of the protonated acetone dimer in the gas phase

2005

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Mass spectrometry-based methods have been employed in order to study the reactions of non- (h(6)/h(6)), half (d(6)/h(6)), and fully (d(6)/d(6)) deuterium labeled protonated dimers of acetone in the gas phase. Neither kinetic nor thermodynamic isotope effects were found. From MIKES experiments (both spontaneous and collision-induced dissociations), it was found that the relative ion yield (m/z 65 vs m/z 59) from the dissociation reaction of half deuterium labeled (d(6)/h(6)) protonated dimer of acetone is dependent on the internal energy. A relative ion yield (m/z 65 vs m/z 59) close to unity is observed for cold, nonactivated, metastable ions, whereas the ion yield is observed to increase (favoring m/z 65) when the pressure of the collision gas is increased. This is in striking contrast to what would be expected if a kinetic isotope effect were present. A combined study of the kinetics and the thermodynamics of the association reaction between acetone and protonated acetone implicates the presence of at least two isomeric adducts. We have employed G3(MP2) theory to map the potential energy surface leading from the reactants, acetone and protonated acetone, to the various isomeric adducts. The proton-bound dimer of acetone was found to be the lowest-energy isomer, and protonated diacetone alcohol the next lowest-energy isomer. Protonated diacetone alcohol, even though it is an isomer hidden behind many barriers, can possibly account for the observed relative ion yield and its dependence on the mode of activation.

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Determination of rate constants for low pressure association reactions by Fourier transform-ion cyclotron resonance spectrometry

Cited by 37 publications

References 19 publications

Radiative Association Kinetics and Binding Energies of Chromium Ions with Benzene and Benzene Derivatives

Radiative Association Kinetics and Binding Energies of Chromium Ions with Benzene and Benzene Derivatives

Structures, energetics, and dynamics of gas phase ions studied by FTICR and HPMS

Isomerization of the protonated acetone dimer in the gas phase

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