Electron affinity

The electron affinity (E_ea) of an atom or molecule is defined as the amount of energy released when an electron attaches to a neutral atom or molecule in the gaseous state to form an anion.

X(g) + e⁻ → X⁻(g) + energy

This differs by sign from the energy change of electron capture ionization.^[1] The electron affinity is positive when energy is released on electron capture.

In solid state physics, the electron affinity for a surface is defined somewhat differently (see below).

This property is used to measure atoms and molecules in the gaseous state only, since in a solid or liquid state their energy levels would be changed by contact with other atoms or molecules.

A list of the electron affinities was used by Robert S. Mulliken to develop an electronegativity scale for atoms, equal to the average of the electrons affinity and ionization potential.^[2][3] Other theoretical concepts that use electron affinity include electronic chemical potential and chemical hardness. Another example, a molecule or atom that has a more positive value of electron affinity than another is often called an electron acceptor and the less positive an electron donor. Together they may undergo charge-transfer reactions.

Although E_ea varies greatly across the periodic table, some patterns emerge. Generally, nonmetals have more positive E_ea than metals. Atoms whose anions are more stable than neutral atoms have a greater E_ea. Chlorine most strongly attracts extra electrons; neon most weakly attracts an extra electron. The electron affinities of the noble gases have not been conclusively measured, so they may or may not have slightly negative values.

E_ea generally increases across a period (row) in the periodic table prior to reaching group 18. This is caused by the filling of the valence shell of the atom; a group 17 atom releases more energy than a group 1 atom on gaining an electron because it obtains a filled valence shell and therefore is more stable. In group 18, the valence shell is full, meaning that added electrons are unstable, tending to be ejected very quickly.

Counterintuitively, E_ea does not decrease when progressing down most columns of the periodic table. For example, E_ea actually increases consistently on descending the column for the group 2 data. Thus, electron affinity follows the same "left-right" trend as electronegativity, but not the "up-down" trend.

The following data are quoted in kJ/mol.

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#d8d8d8; padding: 2px 4px;"}]]}" class="notheme">Electron affinities in the periodic table

Group →	1	2		3	4	5	6	7	8	9	10	11	12	13	14	15	16	17	18
↓ Period
1	H 73																		He(−50)
2	Li60	Be(−50)												B 27	C 122	N −7	O 141	F 328	Ne(−120)
3	Na53	Mg(−40)												Al42	Si134	P 72	S 200	Cl349	Ar(−96)
4	K 48	Ca2		Sc18	Ti7	V 51	Cr65	Mn(−50)	Fe15	Co64	Ni112	Cu119	Zn(−60)	Ga29	Ge119	As78	Se195	Br325	Kr(−96)
5	Rb47	Sr5		Y 30	Zr42	Nb89	Mo72	Tc(53)	Ru(101)	Rh110	Pd54	Ag126	Cd(−70)	In37	Sn107	Sb101	Te190	I 295	Xe(−80)
6	Cs46	Ba14		Lu23	Hf17	Ta31	W 79	Re6	Os104	Ir151	Pt205	Au223	Hg(−50)	Tl31	Pb34	Bi91	Po(136)	At233	Rn(−70)
7	Fr(47)	Ra(10)		Lr(−30)	Rf	Db	Sg	Bh	Hs	Mt	Ds	Rg(151)	Cn(<0)	Nh(67)	Fl(<0)	Mc(35)	Lv(75)	Ts(166)	Og(8)
				La54	Ce55	Pr11	Nd9	Pm(12)	Sm(16)	Eu11	Gd(13)	Tb13	Dy1	Ho(33)	Er(30)	Tm99	Yb(−2)
				Ac(34)	Th(113)	Pa(53)	U (51)	Np(46)	Pu(−48)	Am(10)	Cm(27)	Bk(−165)	Cf(−97)	Es(−29)	Fm(34)	Md(94)	No(−223)
Legend
Values are in kJ/mol, rounded
For the equivalent in eV, see: Electron affinity (data page)
Parentheses or Round brackets() denote predictions
Primordial  From decay  Synthetic Border shows natural occurrence of the element s-block f-block d-block p-block

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The electron affinity of molecules is a complicated function of their electronic structure. For instance the electron affinity for benzene is negative, as is that of naphthalene, while those of anthracene, phenanthrene and pyrene are positive. In silico experiments show that the electron affinity of hexacyanobenzene surpasses that of fullerene.^[5]

In the field of solid state physics, the electron affinity is defined differently than in chemistry and atomic physics. For a semiconductor-vacuum interface (that is, the surface of a semiconductor), electron affinity, typically denoted by E_EA or χ, is defined as the energy obtained by moving an electron from the vacuum just outside the semiconductor to the bottom of the conduction band just inside the semiconductor:^[6]

${\displaystyle E_{\rm {ea}}\equiv E_{\rm {vac}}-E_{\rm {C}}}$

In an intrinsic semiconductor at absolute zero, this concept is functionally analogous to the chemistry definition of electron affinity, since an added electron will spontaneously go to the bottom of the conduction band. At nonzero temperature, and for other materials (metals, semimetals, heavily doped semiconductors), the analogy does not hold since an added electron will instead go to the Fermi level on average. In any case, the value of the electron affinity of a solid substance is very different from the chemistry and atomic physics electron affinity value for an atom of the same substance in gas phase. For example, a silicon crystal surface has electron affinity 4.05 eV, whereas an isolated silicon atom has electron affinity 1.39 eV.

The electron affinity of a surface is closely related to, but distinct from, its work function. The work function is the thermodynamic work that can be obtained by reversibly and isothermally removing an electron from the material to vacuum; this thermodynamic electron goes to the Fermi level on average, not the conduction band edge: ${\displaystyle W=E_{\rm {vac}}-E_{\rm {F}}}$. While the work function of a semiconductor can be changed by doping, the electron affinity ideally does not change with doping and so it is closer to being a material constant. However, like work function the electron affinity does depend on the surface termination (crystal face, surface chemistry, etc.) and is strictly a surface property.

In semiconductor physics, the primary use of the electron affinity is not actually in the analysis of semiconductor–vacuum surfaces, but rather in heuristic electron affinity rules for estimating the band bending that occurs at the interface of two materials, in particular metal–semiconductor junctions and semiconductor heterojunctions.

In certain circumstances, the electron affinity may become negative.^[7] Often negative electron affinity is desired to obtain efficient cathodes that can supply electrons to the vacuum with little energy loss. The observed electron yield as a function of various parameters such as bias voltage or illumination conditions can be used to describe these structures with band diagrams in which the electron affinity is one parameter. For one illustration of the apparent effect of surface termination on electron emission, see Figure 3 in Marchywka Effect.

• Electron-capture mass spectrometry
• Electronegativity
• Electron donor
• Ionization energy — a closely related concept describing the energy required to remove an electron from a neutral atom or molecule
• One-electron reduction
• Valence electron
• Vacuum level