Kinetic-energy release

The total excess energy, Eextot, of the precursor ion relative to the heats of formation of the products in their ground state, comprises the excess energy in the transition state, Eex, plus the activation energy of the reverse reaction, 

Note The importance of KER measurements results from the fact that the potential energy surface between transition state and products of a reaction can be reconstructed. [47] Thus, KER and AE data are complementary in determining the energy of the transition state. 

The observed KER consists of two components, one from ex and one from Eor-This splitting becomes obvious from the fact that even if there is no Eor, a small KER is always observed, thus demonstrating partitioning of Eex between Evib and Etrmis (KER)  

Diatomic molecular ion dissociations represent the only case where energy partitioning is clear as all excess energy of the decomposition has to be converted to translational energy of the products (Eex = Eirms )- For polyatomic ions the partitioning of excess energy can be described by a simple empirical relationship between Eex and the number of degrees of freedom, s [6,54] 

Consequently, Etrans becomes rather small for substantial values of s, e.g., 0.3 eV/(0.44 x 30) = 0.023 eV. Therefore, any observed KER in excess of Etrms must originate from being the only alternative source. [53] The analogous partitioning of Eor is described by  

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The temi action spectroscopy refers to how a particular action , or process, depends on photon energy. For example, the photodissociation of 0 with UV light leads to energetic 0+0 fragments the kinetic energy released has been... 

Figure A3.5.2. The Ar photofragment energy spectmm for the dissociation of fiions at 752.5 mn. The upper scale gives the kinetic energy release in the centre-of-mass reference frame, both parallel and antiparallel to the ion beam velocity vector in the laboratory.

Fig. 7. Total kinetic energy release derived from velocity map images of 0(3P2) and D(2S) fragment atoms following photodissociation of OD at 226 and 243 nm, respectively. The initial vibrational state of OD is determined from energy balance with TKER = hv + E(vib)oD — Do(OD). The bar graphs show the calculated photodissociation yields for OD X2Il(v) at a vibrational temperature of 1700 K. (From Radenovic et al.97)...

However, the idea, that 96 may rearrange to the ortho isomer 93 via substituent migration or valence bond tautomerization, which would enable the CH3 loss to proceed as described in (20), could not be substantiated by experimental facts. For example, the secondary decompositions of the [M—CH3]+ ions formed from 93 and 96 are different with regard to the reaction channels and both the kinetic energy release and peak shapes associated with the reactions of interest. Moreover, the CA spectra of the [M—CH3]+ ions exhibit distinct differences. Thus, the [M—CH3]+ ions posses different ion structures and, consequently, a common intermediate and/or reaction mechanism for the process of methyl elimination from ionized 93 and 96 are very unlikely (22). 

An important example of the application of this method is seen for the case of ammonia. Referring to Figure 13, the measured average kinetic energy release of metastable (NH3)nH+ (n = 4-17) is seen to display a maximum value of... 

Figure 13. A plot of the measured average kinetic energy release < r> during the metastable unimolecular decomposition of (NH3)nH+, n = 4-17, as a function of cluster size. The technique involves use of the reflectron shown in Figure 2a. Taken with permission from ref. 2.

Considerable interest in the subject of C-H bond activation at transition-metal centers has developed in the past several years (2), stimulated by the observation that even saturated hydrocarbons can react with little or no activation energy under appropriate conditions. Interestingly, gas phase studies of the reactions of saturated hydrocarbons at transition-metal centers were reported as early as 1973 (3). More recently, ion cyclotron resonance and ion beam experiments have provided many examples of the activation of both C-H and C-C bonds of alkanes by transition-metal ions in the gas phase (4). These gas phase studies have provided a plethora of highly speculative reaction mechanisms. Conventional mechanistic probes, such as isotopic labeling, have served mainly to indicate the complexity of "simple" processes such as the dehydrogenation of alkanes (5). More sophisticated techniques, such as multiphoton infrared laser activation (6) and the determination of kinetic energy release distributions (7), have revealed important features of the potential energy surfaces associated with the reactions of small molecules at transition metal centers. 

The purpose of this article is to review some of the current endeavors in this developing field. To maintain brevity, the focus is on recent studies carried out in our own laboratory and in conjunction with Professor M.T. Bowers at the University of California at Santa Barbara, with emphasis on the use of kinetic energy release distributions and infrared laser multiphoton excitation to probe potential energy surfaces for the reactions of atomic metal ions with alkenes and alkanes. 

Figure 2. Schematic view of reversed geometry double focusing mass spectrometer used for kinetic energy release measurements.

Figure 8. Characteristic shapes of kinetic energy release distributions for different model potential energy surfaces.

Studies of kinetic energy release distributions have implications for the reverse reactions. Notice that on a Type II surface, the association reaction of ground state MB+ and C to form MA+ cannot occur. In contrast, on a Type I potential energy surface the reverse reaction can occur to give the adduct MA+. Unless another exothermic pathway is available to this species, the reaction will be nonproductive. However, it is possible in certain cases to determine that adduct formation did occur by observation of isotopic exchange processes or collisional stabilization at high pressures. 

Figure 9. Kinetic energy release distributions for several dehydrogenation reactions. Data from reference 38.

In contrast to the results obtained for dehydrogenation reactions, kinetic energy release distributions for alkane elimination processes can usually be fit with phase space theory. Results for the loss of methane from reaction 9 of Co + with isobutane are shown in Figure 10b. In fitting the... 

Figure 10. Comparison of experimetnal kinetic energy release distributions to phase-space calculations for (a) dehydrogenation of n-butane by Co+ and (b) loss of methane in reaction of Co+ with isobutane. Data from reference 38.

The success of the phase space theory in fitting kinetic energy release distributions for exothermic reactions which involve no barrier for the reverse reaction have led to the use of this analysis as a tool for deriving invaluable thermochemical data from endothermic reactions. This is an important addition to the studies of endothermic reactions described above. As an example of these studies, consider the decarbonylation reaction 11 of Co+ with acetone which leads to the formation of the... 

The application of newer methods to studies of gas phase organometallic reactions will lead to the development of routine techniques for determination of the thermochemistry of organometallic species. The examples discussed above demonstrate that an analysis of kinetic energy release distributions for exothermic reactions yields accurate metal ligand bond dissociation energies. This can be extended to include neutrals as well as ions. For example, reaction 15 has been used to determine accurate bond dissociation energies for Co-H and C0-CH3 (57). 

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