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ELECTRON AFFINITIES

Thomas M. Miller

Electron affinity is defined as the energy difference between the lowest (ground) state of the neutral and the lowest state of the corresponding negative ion. The accuracy of electron affinity measurements has been greatly improved since the advent of laser photodetachment experiments with negative ions. Electron affinities can be determined with optical precision, though a detailed understanding of atomic and molecular states and splittings is required to specify the photodetachment threshold corresponding to the electron affinity.Column definitions are as follows.

Column heading	Definition
Z	Atomic number; given only for atom entries
Mol. form.	Atomic or molecular formula; tables for molecular electron affinities are ordered by molecular formula
Name	Name of atom or molecule
Elec. aff.	Electron affinity, in units of eV
Uncert.	Uncertainty of electron affinity value, in units of eV
Method	Measurement technique; see table of techniques given below
Ref.	Source of electron affinity value

Atomic and molecular electron affinities are discussed in two excellent articles reviewing photodetachment studies which appear in Gas Phase Ion Chemistry, Vol. 3, Bowers, M. T., Ed., Academic Press, Orlando, 1984: Chapter 21 by Drzaic, P. S., Marks, J., and Brauman, J. I., “Electron Photodetachment from Gas Phase Negative Ions,” p. 167, and Chapter 22 by Mead, R. D., Stevens, A. E., and Lineberger, W. C., “Photodetachment in Negative Ion Beams,” p. 213. Persons interested in photodetachment details should consult these articles and the critical reviews of Andersen, T., Haugen, H. K., and Hotop, H., J. Phys. Chem. Ref. Data 28, 1511, 1999, Hotop, H., and Lineberger, W. C., J. Phys. Chem. Ref. Data 14, 731, 1985, and Andersen, T., Haugen, H. K., and Hotop, H. J. Phys. Chem. Ref. Data 28, 1511, 1999. For simplicity in the tables below, any electron affinity that was discussed in the articles by Drzaic et al. or Hotop and Lineberger is referenced to these sources, where original references are given.

The development of cluster-ion photodetachment apparatuses has brought an explosion of electron affinity estimates for atomic and molecular clusters. The policy in this tabulation is to list (in this order) the electron affinities for atoms, diatoms, triatoms, and selected polyatomic molecules and clusters. If the adiabatic electron affinity has been determined for a simple cluster, the value is given, but the reader is referred to original sources for higher-order clusters. Additional data on molecular electron affinities may be found in Lias, S. G., Bartmess, J. E., Liebman, J. F., Holmes, J. L., Levin, R. D., and Mallard, W. G., Gas Phase Ion and Neutral Thermochemistry, J. Phys. Chem. Ref. Data 17, (Supplement No. 1), 1988 and on the NIST WebBook at the Internet address http://webbook.nist.gov/.

For the present tabulation, the 2014 CODATA value e/(hc) = 8065.544005 ± 0.000050 cm^–1 eV^–1 (http://physics.nist.gov/constants/) has been used to convert electron affinities from the units used in spectroscopic work, cm^–1, into eV for this table. Experimental measurements have improved to the level that the 25 ppb uncertainty in e/(hc) will make a difference in a few cases. For this reason, very accurate electron affinities will be given in cm^–1 with the relevant references.

Abbreviations used in the tables: calc = calculated value; PT = photodetachment threshold using a lamp as a light source; LPT = laser photodetachment threshold; LPES = laser photoelectron spectroscopy; DA = dissociative attachment; attach = electron attachment/detachment equilibrium; e-scat = electron scattering; kinetic = dissociation kinetics; Knud = Knudsen cell; CT = charge transfer; CD = collisional detachment; and ZEKE = zero electron kinetic energy spectroscopy.

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Electron Affinities of Atoms and Molecules

Z	Mol. form.	Name	Synonym	CAS Reg. No.	Elec. aff./eV	Uncert./eV	Method	Ref.
Continued on next page...
Atoms (Listed by Atomic Number)
1	H	Hydrogen (atomic)		12385-13-6	0.75420817		calc	205
	H	Hydrogen (atomic)		12385-13-6	0.754195	0.000019	LPT	89
	D	Deuterium (atomic)		16873-17-9	0.754593	0.000074	LPT	89
	D	Deuterium (atomic)		16873-17-9	0.75465629		calc	205
	T	Tritium (atomic)		15086-10-9	0.75480545		calc	205
2	He	Helium		7440-59-7	not stable		calc	1
3	Li	Lithium		7439-93-2	0.618049	0.000020	LPT	185
4	Be	Beryllium	Glucinium	7440-41-7	not stable		calc	1
5	B	Boron		7440-42-8	0.279723	0.000025	LPES	191
6	C	Carbon		7440-44-0	1.262119	0.000020	LPT	28
7	N	Nitrogen (atomic)		17778-88-0	not stable		DA	1
8	O	Oxygen (atomic)		17778-80-2	1.4611135	0.0000009	LPT	4
9	F	Fluorine (atomic)		14762-94-8	3.4011897	0.0000024	LPT	227
10	Ne	Neon		7440-01-9	not stable		calc	1
11	Na	Sodium	Natrium	7440-23-5	0.547926	0.000025	LPT	1
12	Mg	Magnesium		7439-95-4	not stable		e-scat	1
13	Al	Aluminum		7429-90-5	0.43283	0.00005	LPES	208
14	Si	Silicon		7440-21-3	1.3895211	0.0000007	LPES	4
15	P	Phosphorus		7723-14-0	0.746607	0.000010	LPT	377

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ELECTRON AFFINITIES

Electron Affinities of Atoms and Molecules

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