Electron affinities radicals

TABLE 4.4 Electron Affinities of Atoms, Molecules, and Radicals Electron affinity of an atom (molecule or radical) is defined as the energy difference between the lowest (ground) state of the neutral and the lowest state of the corresponding negative ion in the gas phase. A(g) + e = A-(g) Data are limited to those negative ions which, by virtue of their positive electron affinity, are stable. Uncertainty in the final data figures is given in parentheses. Calculated values are enclosed in brackets. ... 

Radical Electron affinity, eV Radical Electron affinity, eV ... 

Rodriquez, C. R, Sirois, S., and Hopkinson, A. C. "Effect of Multiple Halide Substituents on the Acidity of Methanes and Methyl Radicals. Electron Affinities of Chloro and Fluoromethyl Radicals."... 

Table 4.4 Electron Affinities of Elements, Molecules, and Radicals...

Several portions of Section 4, Properties of Atoms, Radicals, and Bonds, have been significantly enlarged. For example, the entries under Ionization Energy of Molecular and Radical Species now number 740 and have an additional column with the enthalpy of formation of the ions. Likewise, the table on Electron Affinities of the Elements, Molecules, and Radicals now contains about 225 entries. The Table of Nuclides has material on additional radionuclides, their radiations, and the neutron capture cross sections. 

The polarographic half-wave reduction potential of 4-nitroisothiazole is -0.45 V (pH 7, vs. saturated calomel electrode). This potential is related to the electron affinity of the molecule and it provides a measure of the energy of the LUMO. Pulse radiolysis and ESR studies have been carried out on the radical anions arising from one-electron reduction of 4-nitroisothiazole and other nitro-heterocycles (76MI41704). 

Fig. 1.8. Ionization energy (/) and electron affinity (A) gaps in eV for radicals. [Adapted from R. G. Pearson, J. Am. Chem. Soc. 110 7684 (1988).]...

The electron affinity of radicals is considerably greater than the electron affinity of monomers, hence in the presence of monomer" ions, or in the presence of an excess of the primary electron donors, the dimeric radical ions are rapidly converted into dimeric diions,... 

Luche and coworkers [34] investigated the mechanistic aspects of Diels-Alder reactions of anthracene with either 1,4-benzoquinone or maleic anhydride. The cycloaddition of anthracene with maleic anhydride in DCM is slow under US irradiation in the presence or absence of 5% tris (p-bromophenyl) aminium hexachloroantimonate (the classical Bauld monoelectronic oxidant, TBPA), whereas the Diels Alder reaction of 1,4-benzoquinone with anthracene in DCM under US irradiation at 80 °C is slow in the absence of 5 % TBPA but proceeds very quickly and with high yield at 25 °C in the presence of TBPA. This last cycloaddition is also strongly accelerated when carried out under stirring solely at 0°C with 1% FeCh. The US-promoted Diels Alder reaction in the presence of TBPA has been justified by hypothesizing a mechanism via radical-cation of diene, which is operative if the electronic affinity of dienophile is not too weak. 

In this equation, r) the absolute hardness, is one-half the difference between /, the ionization potential, and A, the electron affinity. The softness, a, is the reciprocal of T]. Values of t) for some molecules and ions are given in Table 8.4. Note that the proton, which is involved in all Brdnsted acid-base reactions, is the hardest acid listed, with t — c (it has no ionization potential). The above equation cannot be applied to anions, because electron affinities cannot be measured for them. Instead, the assumption is made that t) for an anion X is the same as that for the radical Other methods are also needed to apply the treatment to polyatomic... 

Radicals can be prepared from closed-shell systems by adding or removing one electron or by a dissociative fission. Generally speaking, the electron addition or abstraction can be performed with any system, the ionization potential and electron affinity being thermodynamic measures of the probability with which these processes should proceed. Thus, to accomplish this electron transfer, a sufficiently powerful electron donor or acceptor (low ionization potential and high electron affinity, respectively) is required. If the process does not proceed in the gas phase, a suitable solvent may succeed. 

Figure 9. Determination of the first electron affinity, and the first and higher ionization potentials of formyl radical from the SCF orbital energies and electronic repulsion integrals, and K,j (cf. eqs. (90), (92), and (93)). The experimental value (112), 9.88 eV, for the first ionization potential corresponds to the theoretical value I . All entries are given in eV. With A and I a lower index stands for MO the upper one indicates the state multiplicity after ionization.

It is important to note that the above row correlates well with the reduction in chemical activity of the radicals listed [42] but contradicts to, for instance, electronic affinity between some of them [43]. There is no doubt that the results reported provide the evidence in favour of dominating significance of chemical activity of free radicals on their ad-... 

Even in reactions involving excited states or in reactions between two radicals, the primary interaction which determines the reactivity is thought to proceed adiabatically. The probability of nonadiabatic charge transfer also may not be ignored between a molecular specie with small ionization potential and a specie with large electron affinity, in particular in the form of free, gaseous, or nonsolvated state. In that... 

Specific Electron Capture. It is now customary to use solvents such as methanol (usually CD3OD) or methyl tetrahydrofuran (MTHF) as solvents if electron-capture by AB is required. These solvents form good glasses at 77 K, and for sufficiently dilute solutions of the substrate, AB, electron ejection occurs overwhelmingly from solvent molecules, so that AB+ centres are not formed. Electrons are fairly mobile, and hence AB radicals are formed provided AB has, effectively, a positive electron affinity. The hole centres, such as CD30D+, are not mobile because proton transfer to surrounding solvent molecules occurs rapidly at all temperatures. 

For cationic zeolites Richardson (79) has demonstrated that the radical concentration is a function of the electron affinity of the exchangeable cation and the ionization potential of the hydrocarbon, provided the size of the molecule does not prevent entrance into the zeolite. In a study made on mixed cationic zeolites, such as MgCuY, Richardson used the ability of zeolites to form radicals as a measure of the polarizing effect of one metal cation upon another. He subsequently developed a theory for the catalytic activity of these materials based upon this polarizing ability of various cations. It should be pointed out that infrared and ESR evidence indicate that this same polarizing ability is effective in hydrolyzing water to form acidic sites in cationic zeolites (80, 81). 

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