Stabilization collisional

Recombination by collisional stabilization is a process inverse to thermal uni-molecular decay (Chapter V). Consequently, the mechanism of this reaction (the so-called energy transfer mechanism) is 

Just as for unimolecular reactions, the effective rate constant kr of A and B recombination depends on pressure of species M. It can be calculated via kdiss of the reverse process and the equilibrium constant. 

Adopting the mechanism of strong deactivating collisions and neglecting the distribution of AB over energy, the ratio of the rate of molecular [AB] formation is 

It follows from this expression that, at high pressures when k a( ) k, Eq. (19.8) reduces to 

It was assumed above that the quasimolecule is formed from species A and B. However, another mechanism is also possible (mechanism of the complex formation) 

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To detect tlie initial apparent non-RRKM decay, one has to monitor the reaction at short times. This can be perfomied by studying the unimolecular decomposition at high pressures, where collisional stabilization competes with the rate of IVR. The first successful detection of apparent non-RRKM behaviour was accomplished by Rabinovitch and co-workers [115], who used chemical activation to prepare vibrationally excited hexafluorobicyclopropyl-d2 ... 

Aquilante and Volpi indicate (2) that propanium ions formed by proton transfer from H3 + are not collisionally stabilized at propane pressures as great as 0.3 mm. and that they decompose by elimination of hydrogen or a smaller saturated hydrocarbon to form an alkyl carbonium ion. Others (16, 19) have proposed one or the other of these fates for unstabilized propanium ions. Our observations can be rationalized within this framework by the following mechanisms ... 

Photolysis of O3 yields O2 and electronically excited 0( D), which can either be collisionally stabilized (reaction 6.18) or react with a water molecule to yield two hydroxyl radicals (reaction 6.19). Atmospheric concentrations of hydroxyl radical on a 24-h seasonal average basis are estimated at 1 X 10 molecules cm while peak daytime concentrations of 46 X 10 molecules cm have been observed. ... 

Reactants AB+ + CD are considered to associate to form a weakly bonded intermediate complex, AB+ CD, the ground vibrational state of which has a barrier to the formation of the more strongly bound form, ABCD+. The reactants, of course, have access to both of these isomeric forms, although the presence of the barrier will affect the rate of unimolecular isomerization between them. Note that the minimum energy barrier may not be accessed in a particular interaction of AB+ with CD since the dynamics, i.e. initial trajectories and the detailed nature of the potential surface, control the reaction coordinate followed. Even in the absence (left hand dashed line in Figure 1) of a formal barrier (i.e. of a local potential maximum), the intermediate will resonate between the conformations having AB+ CD or ABCD+ character. These complexes only have the possibilities of unimolecular decomposition back to AB+ + CD or collisional stabilization. In the stabilization process,... 

Notes The data clearly illustrate that at the low pressures in the ICR binary channels dominate, but that the intermediate complex is sufficiently long lived to be collisionally stabilized in the higher pressure SIFT experiments. The cyclic isomer, c-C,H(, was unreactive with these reactant neutrals. bAn isomerization reaction to yield c-C,H( also occurs.515-1... 

To identify the isomeric form of the product of the collisionally stabilized analog of reaction 44 experimentally, Scott et al.92 studied reactions of C3H30+ (C2Hj/CO) produced in that reaction and compared it with that produced directly from propynal in an electron impact ion source or by proton transfer from HCO+ to propynal in the flow tube (these latter two production methods yielded ions with... 

The intermediate reaction complexes (after formation with rate constant, fc,), can undergo unimolecular dissociation ( , ) back to the original reactants, collisional stabilization (ks) via a third body, and intermolecular reaction (kT) to form stable products HC0j(H20)m with the concomitant displacement of water molecules. The experimentally measured rate constant, kexp, can be related to the rate constants of the elementary steps by the following equation, through the use of a steady-state approximation on 0H (H20)nC02 ... 

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. 

M2-CO the first adduct bond energies are greater for Co, Ru, Pd, W, Ir, and Pt than V, Fe, Ni, Nb, and Mo. For the trimers, iron has a weaker bond than the other metals studied. For the tetramer and larger clusters the reactivity is controlled by the value of kn and no longer by the competition between uni molecular decomposition and collisional stabilization. The large cluster regime is not covered by this model used to make the correlation between kinetics and energeti cs. 

In condensation reactions, one eventually obtains a product ion of greater molecular weight than the reactant ion through partial stabilization. In the extreme case, complete stabilization may even occur (collisional stabilization). An example is... 

The excited product CHDCD2 can be collisionally stabilized, but can it otherwise dissociate as follows ... 

When formed from thermal electrons at room temperature its lifetime with respect to auto-ionisation is about 25 psec170. Consequently few of these ions could escape collisional stabilization... 

Application of the steady-state approximation to the initially formed, chemically activated complex yields the rate equation for disappearance of the bare chloride ion and formation of the collisionally stabilized Sfj2 intermediate. Equation (7). The apparent bimolecular rate constant for the formation of the stabilized complex... 

Hase s trajectory value for the association rate constant, /cp of 1.04 cm- s maybe used in conjunction with the above Langevin value of the collisional stabilization rate constant to yield a unimolecular dissociation rate constant of 3.75 x 10 ° s and a lifetime of 27 ps. In each case, these values are in excellent agreement with the order of magnitude of lifetimes predicted by Hase s calculations for cr/CHjCl collisions at relative translational energies of 1 kcal mor , rotational temperatures of 300 K, and vibrational energies equal to the zero-point energy of the system. 

A technique that allows rapid evaluation of molecular stability using small (20-30 mg) samples has been demonstrated and applied to three different families of strained molecules. All of the molecules studied are stable at room temperature, though most must be stored in nonmetallic containers to avoid catalytic decomposition. Of the four molecules shown in Fig. 4.1, the least thermally stable was quadricyclane, for which decomposition lifetimes drop below 10 ms at about 500 K. The other three molecules had similar stabilities, with lifetimes dropping below 10 ms above 700 K. For all systems studied, decomposition by loss of small hydrocarbon fragments (acetylene or ethene) was an important decomposition mechanism in the gas phase. For all but AEBCB, isomerization was also a significant decomposition mechanism. At high pressures, one would expect more isomerization because the very rapid collision rate should allow collisional stabilization of the isomerization products. 

Using statistical-dynamical methods and transition state theory, Zhang and co workers demonstrated that excited carbonyls dissociate promptly to prodnce OH radicals (11%) or isomerize to form dioxirane (32%) or are collisionally stabilized (57%) . 

There is increasing evidence that for some reactions, the R02 + NO reaction produces a fraction of the alkoxy radicals with sufficient energy that they decompose immediately. For example, Orlando et al. (1998) observed that in the reaction of OH with C2H4, approximately 25% of the H0CH2CH20 radicals generated in the reaction of H0CH2CH200 with NO decomposed before they could be collisionally stabilized. Similar observations have been made for R02 from the reactions of alternate CFCs (see Chapter 13). 

The collisional stabilization (de-activation) efficiency is assumed to be unity, which is consistent with the strong collision assumption. Thus the stabilization rate constant ks is equal to the hard-sphere rate constant kHS, and Eq. 10.120 becomes... 

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