Examining electron affinities

Return to the case of LiF. Lithium ionizes readily, but has little affinity for electrons (I = ionization energy = 5.4 eV and A = electron affinity = 0eV.). On the other hand, fluorine is difficult to ionize, but has considerable electron affinity (I = 17.4eV. and A = -3.6eV.). Thus, when Li and F atoms are close neighbors, electrons can transfer to make Li+ and I. These then attract electrostatically until compression of their ion-cores prevent them from contracting further. In a solid crystal, there are both attractive +/- pairs, and repulsive (+/+ as well as -/-) pairs. However, for large arrays, there is a net attraction. This can be shown most simply by examining a linear chain of +q, and -q charges (Kittel, 1966). 

We now examine the available experimental evidence in the light of the above discussion. Specifically, we shall consider physical properties such as (a) ionization potentials and (b) electron affinities. 

Electron affinities for 35 substituted nitrobenzenes have been reported and provided a comprehensive data set for the examination of substituent effects38. The data were used to derive Taft gas-phase substituent parameters and discussed qualitatively based on frontier orbital molecular theory38. The rate constants for the exo-energetic electron-transfer reactions were found to be close to those predicted by the ADO (average dipole orientation) theory38. 

The difference in the electron affinity between light and heavy isotopic isomers is, in other words, the difference in the stability of their anion-radicals. Such a difference gives a valuable tool for use in probing the chemistry of anion-radicals. The difference in the stability of the ring-deuterated and ring-nondeuterated arene anion-radicals has been employed to examine the transition states for the one-electron-promoted cleavage of naphthyl methyl phenyl ether and naphthyl benzyl ether (Guthrie and Shi 1990). In this reaction, the potassium salt of fluoranthene anion-radical was an electron donor ... 

To determine how much HF is needed, we consider systems where s is significantly greater than 1, but where GGA still works reasonably well. In Ref. [18], we examined the ionization potentials, electron affinities, and electronegativities of a variety of atoms, as well as the atomization energies of several... 

Structures. - A very comprehensive review of the literature on atomic and molecular electron affinities has been published142. The possibilities of per-fluoroaroinatic molecules as electron acceptors has been examined using a DFT... 

V. D. Parker [56] obtained in acetonitrile the oxidation and reduction potentials (EQx and ERea) of alternant aromatic hydrocarbons (AAH) by cyclic voltammetry and examined how those potentials are related to the ionization potential (IP) and the electron affinity (EA) of the compounds (Table 8.8). As expected, he found linear relations of unit slopes between E0x and IP and between ERed and EA. Moreover, he found that E0x and ERed of each AAH was symmetrical with respect to a common potential MAAH (-0.31 V vs SCE). The values of (E0x-MAAH) and (ERed Maa ) are correlated with the values of IP and EA, obtained in the vacuum, by E0x-Maah = IP- +AGsV+ and ERed-MAAII = liA-r/t-AG, respectively (Fig. 8.21). Here, is the work function of graphite and equal to 4.34 eV, and AGj v+ and AG v are the differences in solvation energies for the 0/+1 and 0/-1 couples of AAH. Experimentally, AG°V+ and AG°V were almost equal, not depending on the species of AAH, and were equal to -1.94 eV in AN. 

A few years ago experimental values were available for Q, S, /, and Z), but not for E the procedure adopted in testing the equation was to use the equation with calculated values of Uq (Equation 13-5) to find E, and as a test of the method to examine the constancy of E for a series of alkali halogenides containing the same halogen. The values obtained in this way were found to be constant to within about 3 kcal/mole. However, later experimental determinations of the values of the electron affinities of the halogen atoms by direct methods have shown that Equation 13-5 for the crystal energy is in general reliable only to about 2 percent. 

D and A are locally excited states). Thus the excitation energies of all the electron transfer states D+A- and D A+ are reduced, and consequently the energy of the frontier orbital D+A state may be relatively much closer to zero than would appear from an examination of the ionization potentials and electron affinities alone. On the other hand Sustmann and Schubert120 found that the logarithm of the rate constant for a number of Diels-Alder reactions was inversely proportional to In—A a, though the points were widely scattered. 

It might be of interest to investigate the reactivity of additional functional groups by examining organic cyanates, thiocyanates, selen-ides, tellurides, phosphines, arsenides and others. All these compounds, which are expected to be reactive towards e q, await investigation that may help to evaluate their electron affinities. 

The electron affinity can also be deduced from the measurement of the spectrum of the photoelectron emission with monochromatic UV light. This technique is ultra-violet (UV) photoelectron emission spectroscopy (or UV photoemission spectroscopy or UPS). The UPS technique involves directing monochromatic UV light to the sample to excite electrons from the valence band into the conduction band of the semiconductor. Since the process occurs near the surface, electrons excited above the vacuum level can be emitted into vacuum. The energy analysis of the photoemitted electrons is the photoemission spectrum. The process is often described in terms of a three step model [8], The first step is the photoexcitation of the valence band electrons into the conduction band, the second step is the transmission to the surface and the third step is the electron emission at the surface. The technique of UPS is probably most often employed to examine the electronic states near the valence band minimum. 

Knowledge of the gas phase electron affinities for a series of molecules, such as the fluoroethylenes, provides new insight into substituent effects. The correlation between the trends in the singlet and triplet excitation energies of the neutral molecules and the quantity (IP - EA) is also examined. 

---