Negative electron affinity

Negative ions also have two unique thennodynainic quantities associated with them the electron affinity, EA, defined as the negative of the enthalpy change for addition of an electron to a molecule at 0 K [117. 121. 122]... 

Miller T M, Leopold D G, Murray K K and Lineberger W C 1986 Electron affinities of the alkali halides and the structure of their negative ions J. Chem. Phys. 85 2368-75... 

So, within the limitations of the single-detenninant, frozen-orbital model, the ionization potentials (IPs) and electron affinities (EAs) are given as the negative of the occupied and virtual spin-orbital energies, respectively. This statement is referred to as Koopmans theorem [47] it is used extensively in quantum chemical calculations as a means for estimating IPs and EAs and often yields results drat are qualitatively correct (i.e., 0.5 eV). 

A Hbasis functions provides K molecular orbitals, but lUJiW of these will not be occupied by smy electrons they are the virtual spin orbitals. If u c were to add an electron to one of these virtual orbitals then this should provide a means of calculating the electron affinity of the system. Electron affinities predicted by Konpman s theorem are always positive when Hartree-Fock calculations are used, because fhe irtucil orbitals always have a positive energy. However, it is observed experimentally that many neutral molecules will accept an electron to form a stable anion and so have negative electron affinities. This can be understood if one realises that electron correlation uDiild be expected to add to the error due to the frozen orbital approximation, rather ihan to counteract it as for ionisation potentials. 

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. ... 

To calculate electron production must be balanced against electron depletion. Free electrons in the gas can become attached to any of a number of species in a combustion gas which have reasonably large electron affinities and which can readily capture electrons to form negative ions. In a combustion gas, such species include OH (1.83 eV), O (1.46 eV), NO2 (3.68 eV), NO (0.09 eV), and others. Because of its relatively high concentration, its abUity to capture electrons, and thus its abUity to reduce the electrical conductivity of the gas, the most important negative ion is usuaUyOH . 

The common characteristics of the above mentioned heterocycles are electron withdrawing and a site of unsaturation that can stabilize the negative charge developed by the displacement reaction through resonance. For example, the thiazole activated halo displacement is similar to that of a conventional activating group as shown in Scheme 1. The activation is derived from the electron affinity and the stabilization of the negative... 

The energy change of reaction (12) is called the electron affinity of the fluorine atom. It is symbolized by E and, as defined here, is a negative quantity if heat is released when the ion is formed ... 

Whether the second step does take place depends on a number of factors. The electron affinity of the M ion must be sufficiently great, and this point can be appreciated by considering a few examples. Electron transfer to stilbene or tetraphenyl ethylene leads to the formation of negative ions which in turn rapidly ac-... 

The electron affinity of carbon is greater than that of nitrogen indeed, the latter is negative. Suggest a reason for this observation. 

Write the electron gain enthalpy of Cl as the negative of the electron affinity (Fig. 1.54 or Appendix 2D). 

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