Radiative association kinetics

Cheng Y-W and Dunbar R C 1995 Radiative association kinetics of methyl-substituted benzene ions J. Rhys. Chem. 99 10 802-7... 

Again the radiative association kinetics described above allow a direct comparison for some realistic values of k and k. For most chemically activated systems at the threshold for unimolecular dissociation, the observed radiative rate constants are of the order of 10-100 s and hence are much below the values expected for k of about 10 s . Therefore, the first limit is most likely to be valid, with the interesting conclusion that the observed unimolecular dissociation rate constant will depend only on the photon density and the absorption cross section (rate constant) at a given wavelength. 

Table 5. Binding Energies Ei, for the Methyl-Substituted Benzene Dimer Cations Based on Application of the Generic Standard Hydrocarbon Model to the Radiative Association Kinetic Data. I obs is the Efficiency per Collision of Radiative...

The Mg+—CeHe dissociation energy at 0 K was determined to be 134 4 kJmol (1.39 0.10 eV) using collision induced dissociation and 112 kJmoH by laser photodissociation . Using the radiative association kinetics approach to ion cyclotron resonance spectrometry, the value was shown to be the comparable 1.61 eV (155 kJmoU ). It was also shown that the binding of the second benzene to Mg , i.e. the Mg+ (CeHe)—CgHe bond energy, is less than 1.4 eV (135 kJmoU ). 

Guo and Castleman s value for the bond enthalpy is consistent with their value for equation 19. Chen and Armentrout s value is consistent with other values in their paper (see Table 5 for a collection of these and other values). From analysis of radiative association kinetics of their Fourier transform ion cyclotron resonance results, Klippenstein, Dunbar and their coworkers46 derived first Ag+ 2-pentene and isoprene binding energies of (154 29) and (174 29) kJmol-1, and second energies of (164 29) and... 

To date, the radiative association kinetics (RAK) technique has been applied to bond formation between metal cations and relatively simple molecules. The consistency of the results observed from different models suggests uncertainties of about 10-15 kJ mol ... 

Dunbar, R.C. (1997) Modeling radiative association kinetics. Int. J. Mass Spectrom. Ion Processes, 160, 1-16. 

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