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Electron affinity (data page)

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Main article: Electron affinity

This page deals with the electron affinity as a property of isolated atoms or molecules (i.e. in the gas phase). Solid state electron affinities are not listed here.

Elements

Electron affinity can be defined in two equivalent ways. First, as the energy that is released by adding an electron to an isolated atom (gas phase). (The energy -or electron affinity- is a scalar quantity and the direction of that energy -released- defines a reaction for which the change in energy ΔE is a negative quantity). The electron affinity is also defined in the case of electron capture as E(initial) – E(final) in order to maintain the positive value.[1] The reverse definition is that the electron affinity is the energy required to remove an electron from a gaseous anion (still a positive quantity, but in which the change in energy ΔE is also a positive quantity). Either convention can be used in practice, but must be consistent in according a scalar, i.e. positive number to the electron affinity.

Negative electron affinities can be used in those cases where electron capture requires energy, i.e. when capture can occur only if the impinging electron has a kinetic energy large enough to excite a resonance of the atom-plus-electron system. Conversely electron removal from the anion formed in this way releases energy, which is carried out by the freed electron as kinetic energy. Negative ions formed in these cases are always unstable. They may have lifetimes of the order of microseconds to milliseconds, but they invariably autodetach after some time. The listed value in the table corresponds to a selected low-lying metastable state, which may or may not be the lowest energy resonance. For example, in He− there is a metastable state with 0.359 ms lifetime at 19.7 eV above the ground state of He, however there is also a lower energy resonance at 19.4 eV that only has a 10−13 s lifetime.[2]

Z Element Name Electron affinity (eV) Electron affinity (kJ/mol) References
1 1H Hydrogen 0.754 195(19) 72.769(2) [3]
2D Deuterium 0.754 59(8) 72.807(8)
2 He Helium -19.7 1s2s2p 4P5/2, 350 μs lifetime.[2]
3 Li Lithium 0.618 049(22) 59.6326(21) [4]
4 Be Beryllium -2.4 1s2s2p2 4P3/2, 43 μs lifetime.[2]
5 B Boron 0.279 723(25) 26.989(3) [5]
6 12C Carbon 1.262 122 6(11) 121.776 3(1) [6]
13C 1.262 113 6(12) 121.775 5(2)
7 N Nitrogen -1.4 2p4 1D, <1 μs lifetime.[2]
8 16O Oxygen 1.461 1136(9) 140.9760(2) [7]
17O 1.461 108(4) 140.9755(4) [8]
18O 1.461 105(3) 140.9752(3)
9 F Fluorine 3.401 1898(25) 328.1649(3) [9][10]
10 Ne Neon - no metastable states[2]
11 Na Sodium 0.547 926(25) 52.867(3) [11]
12 Mg Magnesium - no metastable states[2]
13 Al Aluminium 0.432 83(5) 41.762(5) [12]
14 Si Silicon 1.389 5212(8) 134.0684(1) [7]
15 P Phosphorus 0.746 607(10) 72.037(1) [13]
16 32S Sulfur 2.077 1042(6) 200.4101(1) [7]
34S 2.077 1045(12) 200.4101(2) [14]
17 Cl Chlorine 3.612 724(27) 348.575(3) [15]
18 Ar Argon -11.5 3p54s4p 4S3/2, 260 ns lifetime[2]
19 K Potassium 0.501 459(13) 48.383(2) [16]
20 Ca Calcium 0.024 55(10) 2.37(1) [17]
21 Sc Scandium 0.188(20) 18(2) [18]
22 Ti Titanium 0.084(9) 8(1) [19]
23 V Vanadium 0.527 66(20) 50.911(20) [20]
24 Cr Chromium 0.675 84(12) 65.21(2) [21]
25 Mn Manganese -1 (theoretical) [2]
26 Fe Iron 0.153 236(34) 14.785(4) [22]
27 Co Cobalt 0.662 26(5) 63.898(5) [23]
28 Ni Nickel 1.157 16(12) 111.65(2) [24]
29 Cu Copper 1.235 78(4) 119.235(4) [21]
30 Zn Zinc - No stable negative ion.[2]
31 Ga Gallium 0.43(3) 41(3) [25]
32 Ge Germanium 1.232 6764(13) 118.9352(2) [26]
33 As Arsenic 0.8048(2) 77.65(2) [27]
34 Se Selenium 2.020 6047(12) 194.9587(2) [28]
35 Br Bromine 3.363 588(3) 324.5370(3) [9]
36 Kr Krypton - no metastable states[2]
37 Rb Rubidium 0.485 916(21) 46.884(3) [29]
38 Sr Strontium 0.052 06(6) 5.023(6) [30]
39 Y Yttrium 0.307(12) 29.6(12) [18]
40 Zr Zirconium 0.427(14) 41.2(14) [31]
41 Nb Niobium 0.91740(6) 88.516(7) [32]
42 Mo Molybdenum 0.7473(3) 72.10(3) [21]
43 Tc Technetium ? May be unstable like Mn.[2]
44 Ru Ruthenium 1.046 38(25) 100.96(3) [33]
45 Rh Rhodium 1.142 89(20) 110.27(2) [24]
46 Pd Palladium 0.562 14(12) 54.24(2)
47 Ag Silver 1.304 47(3) 125.862(3) [21]
48 Cd Cadmium - No stable negative ion.[2]
49 In Indium 0.383 92(6) 37.043(6) [34]
50 Sn Tin 1.112 070(2) 107.2984(3) [35]
51 Sb Antimony 1.047 401(19) 101.059(2) [36]
52 Te Tellurium 1.970 875(7) 190.161(1) [37]
53 I Iodine 3.059 0465(38) 295.1531(4) [38]
54 Xe Xenon -0.056(10) (theoretical) [2]
55 Cs Caesium 0.471 630(25) 45.505(3) [11][39]
56 Ba Barium 0.144 62(6) 13.954(6) [40]
57 La Lanthanum 0.55(2) 53(2) [41]
58 Ce Cerium 0.57(2) 55(2) [42]
59 Pr Praseodymium 0.962(24) 93(3) [2]
60 Nd Neodymium 0.162 (theoretical) [43]
61 Pm Promethium 0.129 (theoretical)
62 Sm Samarium 0.162 (theoretical)
63 Eu Europium 0.116(13) 11(1) [44]
64 Gd Gadolinium 0.137 (theoretical) [43]
65 Tb Terbium 0.436 (theoretical)
66 Dy Dysprosium 0.352 (theoretical)
67 Ho Holmium 0.338 (theoretical)
68 Er Erbium 0.312 (theoretical)
69 Tm Thulium 1.029(22) 99(3) [45]
70 Yb Ytterbium 0.00(3) [2]
71 Lu Lutetium 0.346(14) 33.4(15) [46][47]
72 Hf Hafnium 0.114 (theoretical) [2][48]
73 Ta Tantalum 0.323(12) 31(2) [31]
74 W Tungsten 0.816 26(8) 78.76(1) [49]
75 Re Rhenium 0.15(10) 14(10) [50] May be unstable like Mn.[2]
76 Os Osmium 1.077 80(12) 103.99(2) [51]
77 Ir Iridium 1.564 36(15) 150.94(2) [52]
78 Pt Platinum 2.125 10(5) 205.041(5)
79 Au Gold 2.308 610(25) 222.747(3) [53]
80 Hg Mercury - No stable negative ion.[2]
81 Tl Thallium 0.377(13) 36.4(14) [54]
82 Pb Lead 0.364(8) 35(1) [55]
83 Bi Bismuth 0.942 362(13) 90.924(2) [56]
84 Po Polonium 1.405(62) (theoretical) 135.5(60) (theoretical) [57]
85 At Astatine 2.42(12) (theoretical) 233.1(11) (theoretical)
86 Rn Radon
87 Fr Francium 0.491(5) (theoretical) [58]
88 Ra Radium
89 Ac Actinium
90 Th Thorium
91 Pa Protactinium
92 U Uranium
93 Np Neptunium
94 Pu Plutonium
95 Am Americium
96 Cm Curium
97 Bk Berkelium
98 Cf Californium
99 Es Einsteinium
100 Fm Fermium
101 Md Mendelevium
102 No Nobelium
103 Lr Lawrencium
104 Rf Rutherfordium
105 Db Dubnium
106 Sg Seaborgium
107 Bh Bohrium
108 Hs Hassium
109 Mt Meitnerium
110 Ds Darmstadtium
111 Rg Roentgenium
112 Cn Copernicium
113 Nh Nihonium
114 Fl Flerovium
115 Mc Moscovium
116 Lv Livermorium
117 Ts Tennessine 2.6 or 1.8 (theoretical) [59]
118 Og Oganesson 0.056(10) (theoretical) [60]
119 Uue Ununennium 0.662 (theoretical) [58]
120 Ubn Unbinilium

Molecules

The electron affinities Eea of some molecules are given in the table below, from the lightest to the heaviest. Many more have been listed by Rienstra-Kiracofe et al. (2002). The electron affinities of the radicals OH and SH are the most precisely known of all molecular electron affinities.

Molecule Name Eea (eV) Eea (kJ/mol) References
Diatomics
16OH Hydroxyl 1.827 6488(11) 176.3413(2) Goldfarb et al. (2005)
16OD 1.825 53(4) 176.137(5) Schulz et al. (1982)
C2 Dicarbon 3.269(6) 315.4(6) Ervin & Lineberger (1991)
BO Boron oxide 2.508(8) 242.0(8) Wenthold et al. (1997)
NO Nitric oxide 0.026(5) 2.5(5) Travers, Cowles & Ellison (1989)
O2 Dioxygen 0.450(2) 43.42(20) Schiedt & Weinkauf (1995)
32SH Sulfhydryl 2.314 7283(17) 223.3373(2) Chaibi et al. (2006)
F2 Difluorine 3.08(10) 297(10) Janousek & Brauman (1979)
Cl2 Dichlorine 2.35(8) 227(8) Janousek & Brauman (1979)
Br2 Dibromine 2.53(8) 244(8) Janousek & Brauman (1979)
I2 Diiodine 2.524(5) 243.5(5) Zanni et al. (1997)
IBr Iodine bromide 2.512(3) 242.4(4) Sheps, Miller & Lineberger (2009)
LiCl Lithium chloride 0.593(10) 57.2(10) Miller et al. (1986)
FeO Iron(II) oxide 1.4950(5) 144.25(6) Kim, Weichman & Neumark (2015)
Triatomics
NO2 Nitrogen dioxide 2.273(5) 219.3(5) Ervin, Ho & Lineberger (1988)
O3 Ozone 2.1028(25) 202.89(25) Novick et al. (1979)
SO2 Sulfur dioxide 1.107(8) 106.8(8) Nimlos & Ellison (1986)
Larger polyatomics
CH2CHO Vinyloxy 1.8248(+2-6) 176.07(+3-7) Rienstra-Kiracofe et al. (2002) after Mead et al. (1984)
C6H6 Benzene -0.70(14) −68(14) Ruoff et al. (1995)
C6H4O2 p-Benzoquinone 1.860(5) 179.5(6) Schiedt & Weinkauf (1999)
BF3 Boron trifluoride 2.65(10) 256(10) Page & Goode (1969)
HNO3 Nitric acid 0.57(15) 55(14) Janousek & Brauman (1979)
CH3NO2 Nitromethane 0.172(6) 16.6(6) Adams et al. (2009)
POCl3 Phosphoryl chloride 1.41(20) 136(20) Mathur et al. (1976)
SF6 Sulfur hexafluoride 1.03(5) 99.4(49) Troe, Miller & Viggiano (2012)
C2(CN)4 Tetracyanoethylene 3.17(20) 306(20) Chowdhury & Kebarle (1986)
WF6 Tungsten hexafluoride 3.5(1) 338(10) George & Beauchamp (1979)
UF6 Uranium hexafluoride 5.06(20) 488(20) NIST chemistry webbook after Borshchevskii et al. (1988)
C60 Buckminsterfullerene 2.6835(6) 258.92(6) Huang et al. (2014)

Bibliography

  • Janousek, Bruce K.; Brauman, John I. (1979), "Electron affinities", in Bowers, M. T. (ed.), Gas Phase Ion Chemistry, vol. 2, New York: Academic Press, p. 53.
  • Rienstra-Kiracofe, J.C.; Tschumper, G.S.; Schaefer, H.F.; Nandi, S.; Ellison, G.B. (2002), "Atomic and molecular electron affinities: Photoelectron experiments and theoretical computations", Chem. Rev., vol. 102, pp. 231–282, doi:10.1021/cr990044u.
  • Updated values can be found in the NIST chemistry webbook. These values must be taken with caution, however, for the Electron affinity determinations tables of this webbook show unexplained differences with respect to the original measurements. For instance the electron affinity of the iodine atom is told to be 3.05900(10) eV according to the most precise measurement, despite the fact the original publication[38] gives 3.0590463(38) eV.

Specific molecules

  • Adams, C.L.; Schneider, H.; Ervin, K.M.; Weber, J.M. (2009), "Low-energy photoelectron imaging spectroscopy of nitromethane anions: Electron affinity, vibrational features, anisotropies, and the dipole-bound state", J. Chem. Phys., 130: 074307, doi:10.1063/1.3076892
  • Borshchevskii, A.Ya.; Boltalina, O.V.; Sorokin, I.D.; Sidorov, L.N. (1988), "Thermochemical quantities for gas-phase iron, uranium, and molybdenum fluorides, and their negative ions", J. Chem. Thermodyn., 20 (5): 523, doi:10.1016/0021-9614(88)90080-8
  • Chaibi, W.; Delsart, C.; Drag, C.; Blondel, C. (2006), "High precision measurement of the 32SH electron affinity by laser detachment microscopy", J. Mol. Spectrosc., 239: 11, doi:10.1016/j.jms.2006.05.012
  • Chowdhury, S.; Kebarle, P. (1986), "Electron affinities of di- and tetracyanoethylene and cyanobenzenes based on measurements of gas-phase electron-transfer equilibria", J. Am. Chem. Soc., 108: 5453, doi:10.1021/ja00278a014
  • Ervin, K.M.; Ho, J.; Lineberger, W.C. (1988), "Ultraviolet photoelectron spectrum of nitrite anion", J. Phys. Chem., 92: 5405, doi:10.1021/j100330a017
  • Ervin, K.M.; Lineberger, W.C. (1991), "Photoelectron spectra of C−
    2     and C2H−", J. Phys. Chem., 95: 1167, doi:10.1021/j100156a026
  • George, P.M.; Beauchamp, J.L. (1979), "The electron and fluoride affinities of tungsten hexafluoride by ion cyclotron resonance spectroscopy", Chem. Phys., 36: 345, doi:10.1016/0301-0104(79)85018-1
  • Goldfarb, F.; Drag, C.; Chaibi, W.; Kröger, S.; Blondel, C.; Delsart, C. (2005), "Photodetachment microscopy of the P, Q, and R branches of the OH−(v=0) to OH(v=0) detachment threshold", J. Chem. Phys, 122: 014308, doi:10.1063/1.1824904
  • Huang, Dao-Ling; Dau, Phuong Diem; Liu, Hong-Tao; Wang, Lai-Sheng (2014), "High-resolution photoelectron imaging of cold C−
    60     anions and accurate determination of the electron affinity of C60", J. Chem. Phys., 140: 224315, doi:10.1063/1.4881421
  • Kim, J.B.; Weichman, M.L.; Neumark, D.M. (2015), "Low-lying states of FeO and FeO− by slow photoelectron spectroscopy", Mol. Phys., 113: 2105, doi:10.1080/00268976.2015.1005706
  • Mathur, B.P.; Rothe, E.W.; Tang, S.Y.; Reck, G.P. (1976), "Negative ions from phosphorus halides due to cesium charge exchange", J. Chem. Phys., 65: 565, doi:10.1063/1.433109
  • Mead, R.D.; Lykke, K.R.; Lineberger, W.C.; Marks, J.; Brauman, J.I. (1984), "Spectroscopy and dynamics of the dipole‐bound state of acetaldehyde enolate", J. Chem. Phys., 81: 4883, doi:10.1063/1.447515
  • Miller, T.M.; Leopold, D.G.; Murray, K.K.; Lineberger, W.C. (1986), "Electron affinities of the alkali halides and the structure of their negative ions", J. Chem. Phys., 85: 2368, doi:10.1063/1.451091
  • Nimlos, Mark R.; Ellison, G. Barney (1986), "Photoelectron spectroscopy of sulfur-containing anions (SO−
    2    , S−
    3    , and S2O−)", J. Phys. Chem., 90: 2574, doi:10.1021/j100403a007
  • Novick, S.E.; Engelking, P.C.; Jones, P.L.; Futrell, J.H.; Lineberger, W.C. (1979), "Laser photoelectron, photodetachment, and photodestruction spectra of O−
    3    ", J. Chem. Phys., 70: 2652, doi:10.1063/1.437842
  • Page, F. M.; Goode, G. C. (1969), Negative ions and the magnetron, John Wiley & Sons[61]
  • Ruoff, R.S.; Kadish, K.M.; Boulas, P.; Chen, E.C.M. (1995), "Relationship between the Electron Affinities and Half-Wave Reduction Potentials of Fullerenes, Aromatic Hydrocarbons, and Metal Complexes", J. Phys. Chem., 99: 8843, doi:10.1021/j100021a060
  • Schiedt, J.; Weinkauf, R. (1995), "Spin-orbit coupling in the O−
    2     anion", Z. Naturforsch. A, 50 (11): 1041, doi:10.1515/zna-1995-1110
  • Schiedt, J.; Weinkauf, R. (1999), "Resonant photodetachment via shape and Feshbach resonances: p-benzoquinone anions as a model system", J. Chem. Phys., 110: 304, doi:10.1063/1.478066
  • Schulz, P.A.; Mead, R.D.; Jones, P.L.; Lineberger, W.C. (1982), "OH− and OD− threshold photodetachment", J. Chem. Phys., 77: 1153, doi:10.1063/1.443980
  • Sheps, L.; Miller, E.M.; Lineberger, W.C. (2009), "Photoelectron spectroscopy of small IBr−(CO2)n(n=0–3) cluster anions", J. Chem. Phys., 131: 064304, doi:10.1063/1.3200941
  • Travers, M.J.; Cowles, D.C.; Ellison, G.B. (1989), "Reinvestigation of the electron affinities of O2 and NO", Chem. Phys. Lett., 164: 449, doi:10.1016/0009-2614(89)85237-6
  • Troe, J.; Miller, T.M.; Viggiano, A.A. (2012), "Revised electron affinity of SF6 from kinetic data", J. Chem. Phys., 136: 121102, doi:10.1063/1.3698170
  • Wenthold, P.G.; Kim, J.B.; Jonas, K.-L.; Lineberger, W.C. (1997), "An Experimental and Computational Study of the Electron Affinity of Boron Oxide", J. Phys. Chem. A, 101: 4472, doi:10.1021/jp970645u
  • Zanni, M.T.; Taylor, T.R.; Greenblatt, B.J.; Soep, B.; Neumark, D.M. (1997), "Characterization of the I−
    2     anion ground state using conventional and femtosecond photoelectron spectroscopy", J. Chem. Phys., 107: 7613, doi:10.1063/1.475110

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See also

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