Affinity, electronic

S = Heat of sublimation of sodium D = Dissociation energy of chlorine / = Ionization energy of sodium = Electron affinity of chlorine Uq = Lattice energy of sodium chloride AHf = Heat of formation of sodium chloride. 

Electron affinities may be estimated using a Born-Haber cycle. 

Fig. V-14. Energy level diagram and energy scales for an n-type semiconductor pho-toelectrochemical cell Eg, band gap E, electron affinity work function Vb, band bending Vh, Helmholtz layer potential drop 0ei. electrolyte work function U/b, flat-band potential. (See Section V-9 for discussion of some of these quantities. (From Ref. 181.)...

Figure A3.5.4. The 488 mn photoelectron spectrum of NaClT The arrow marks the origin band, for transitions from NaCr (v = 0) to NaCl (v = 0), from which the electron affinity of NaCl is obtained.

NaCC) = 2.497 A, and = 0.195 cnV Finally, the position of the origin peak gives the electron binding energy (the electron affinity of NaCl, 0.727 eV) and a themiochemical cycle allows one to calculate the bond... 

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... 

Because NH has an electron affinity of 0.4 eV, the total energies of the above two states can be equal only if the kinetic energy KE carried away by the ejected electron obeys... 

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). 

Simons J 1973 Theory of electron affinities of small molecules J. Chem. Phys. 58 4899-907... 

The spherical shell model can only account for tire major shell closings. For open shell clusters, ellipsoidal distortions occur [47], leading to subshell closings which account for the fine stmctures in figure C1.1.2(a ). The electron shell model is one of tire most successful models emerging from cluster physics. The electron shell effects are observed in many physical properties of tire simple metal clusters, including tlieir ionization potentials, electron affinities, polarizabilities and collective excitations [34]. 

Figure Cl. 1.3 shows a plot of tire chemical reactivity of small Fe, Co and Ni clusters witli FI2 as a function of size (full curves) [53]. The reactivity changes by several orders of magnitudes simply by changing tire cluster size by one atom. Botli geometrical and electronic arguments have been put fortli to explain such reactivity changes. It is found tliat tire reactivity correlates witli tire difference between tire ionization potential (IP) and tire electron affinity...

There is a great number of mostly covalent and tetraliedral binary IV-IV, III-V, II-VI and I-VII semiconductors. Most crystallize in tire zincblende stmcture, but some prefer tire wairtzite stmcture, notably GaN [H, 12]. Wlrile tire bonding in all of tliese compounds (and tlieir alloys) is mostly covalent, some ionic character is always present because of tire difference in electron affinity of tire constituent atoms. 

Much of tills chapter concerns ET reactions in solution. However, gas phase ET processes are well known too. See figure C3.2.1. The Tiarjioon mechanism by which halogens oxidize alkali metals is fundamentally an electron transfer reaction [2]. One might guess, from tliis simple reaction, some of tlie stmctural parameters tliat control ET rates relative electron affinities of reactants, reactant separation distance, bond lengtli changes upon oxidation/reduction, vibrational frequencies, etc. 

Typical elements in Groups V. VI and VII would be expected to achieve a noble gas configuration more easily by gaining electrons rather than losing them. Electron affinity is a measure of the energy change when an atom accepts an extra electron. It is difficult to measure directly and this has only been achieved in a few cases more often it is obtained from enthalpy cycle calculations (p. 74). 

Atomic number Element Atomic radius (g) (nm) Radius ofX ion (nm) Electron affinity (kJ mol )... 

Atomic number Element Electron affinity kJ mol ) Total... 

Table 2.6 shows the electron affinities, for the addition of one electron to elements in Periods 2 and 3. Energy is evolved by many atoms when they accept electrons. In the cases in which energy is absorbed it will be noted that the new electron enters either a previously unoccupied orbital or a half-filled orbital thus in beryllium or magnesium the new electron enters the p orbital, and in nitrogen electron-pairing in the p orbitals is necessary. 

Tables 2.1, 2.2, 2.3 and 2.4 give data for atomic radii, ionisation energies and electron affinities which allow these rough rules to be justified.

AI14 electron affinity of chlorine, x 2 (two ions are formed) —728 A/15 calculated lattice energy —2539... 

The electronic configuration of each halogen is one electron less than that of a noble gas, and it is not surprising therefore, that all the halogens can accept electrons to form X" ions. Indeed, the reactions X(g) + e - X (g), are all exothermic and the values (see Table 11.1), though small relative to the ionisation energies, are all larger than the electron affinity of any other atom. 

One surprising physical property of fluorine is its electron affinity which, at — 333 kJmoPS is lower than that of chlorine, -364 kJmol , indicating that the reaction X(g) + -> X (g) is more... 

Electron affinity and hydration energy decrease with increasing atomic number of the halogen and in spite of the slight fall in bond dissociation enthalpy from chlorine to iodine the enthalpy changes in the reactions... 

Bromine has a lower electron affinity and electrode potential than chlorine but is still a very reactive element. It combines violently with alkali metals and reacts spontaneously with phosphorus, arsenic and antimony. When heated it reacts with many other elements, including gold, but it does not attack platinum, and silver forms a protective film of silver bromide. Because of the strong oxidising properties, bromine, like fluorine and chlorine, tends to form compounds with the electropositive element in a high oxidation state. 

In this equation, the electronegativity of an atom is related to its ionization potential, 1, and its electron affinity, E. Mulhken already pointed out that in this definition the ionization potential, and the electron affinity, E, of valence states have to be used. This idea was further elaborated by Hinze et al. [30, 31], who introduced the concept of orbital electronegativity. 

Values for these coefficients, a, b, c, of Eq. (12) can be obtained from the ionization potentials and electron affinities of the neutral, the cationic, and the anionic states of an orbital. 

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