4.1 Electrons in atoms
4.1.1 Arrangement of electrons in atoms
In the following table the electrons in an atom are
shown arranged in shells and sub-shells. The charge of the nucleus is +
Ze (Z = atomic number), and it is surrounded by Z
electrons (charge −e) in a neutral atom.
Shells
The electrons with the same principal quantum number
n are said to form a shell. Proceeding from the nucleus outwards the
shells are called K, L, etc. Thus if n = 1, 2, 3, 4, the shell is the K,
L, M or N shell, respectively. This nomenclature had its origin in X-ray
spectroscopy, in which a K-series line is due to an electron transition from an
outer to the K shell.
Sub-shells. The electrons in each shell are
arranged in sub-shells (often also called shells), specified by the value of
l (l = 0,1 ,..., n − 1). In Bohr's theory, n
and l determine the size and shape of the orbit. The nl sub-shell
is complete or closed when it contains 2(2l +1) electrons.
Quantum numbers for one electron
These are a development of those introduced by Bohr and
Sommerfeld.
Principal quantum number n, in Bohr's
theory of the H atom, specifies the radius of the orbit and determines the
energy E = − Rhc/n2 where R is the
Rydberg constant. In general, the orbits with any given value of l are
still numbered serially by n, starting with n = l + 1
(circular orbit), but the energy now depends on l too. In wave
mechanics, n − l − 1 is the number of nodes (zeros)
in the radial factor in the wave function.
Azimuthal quantum number l specifies the
angular momentum lh/2π of
the orbital motion, and is connected with the kind of symmetry possessed by the
wave function (l = 0 implies spherical symmetry). Code letters for the
value of l are:
|
l = |
0 |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
|
Code letter |
s |
p |
d |
f |
g |
h |
i |
k |
and so on, omitting j (not used) and s, p (used out of
turn). The value of the principal quantum number n is put in front of
the code letter, e.g. 3d meaning n = 3, l = 2.
Magnetic quantum number ml
specifies one component of the orbital angular momentum:
mlh/2π is the
moment of momentum about some given line through the nucleus, e.g. drawn
parallel to an external magnetic field. The 2l + 1 possible values of
ml are l, (l − 1),...,
−l.
Spin quantum number ms
specifies the component of the intrinsic angular momentum (spin) of the
electron; ms = ± . The third and fourth quantum numbers
are often of less direct significance owing to coupling effects.
Pauli’s Exclusion Principle states that no
two electrons can have all their four quantum numbers the same.
Several electrons: spectral terms
In atoms with many electrons, it is usually a good
approximation to assign values of (n, l) to each electron, corresponding
to motion in an effective central field. Thus
1s22s22p5 means a configuration with
two electrons in the K-shell, two with n = 2 and l = 0, and five
with n = 2 and l = 1. LS coupling. With the lighter
atoms and with outer electrons, the energy of the various possible terms in any
configuration depends on the probability of two electrons being found close
together; and this in turn depends on the vector sums L
= Σ l and S = Σ
s. The magnitude of L is specified by a capital
letter (S, P, D...), and the resultant spin S is specified by writing
the number 2S + 1 as a superscript: the relative orientation of
L and S merely affects the
magnetic energy and splits the terms into 2S + 1 (or fewer) levels. Thus
a term with L = 2 and S = 1 is written 3D (read
‘triplet D’). Note that S is used in two senses, both as a code
letter and as the resultant of spins.
Inner quantum number J specifies the total angular
momentum J = L + S, and is written as
a subscript (3D3, 3D2,
3D1).
X-ray spectra and jj coupling. With inner electrons or
with heavy atoms, the coupling of the spin and orbital magnetic moments
commonly makes it necessary to divide the nl ‘orbits’ into
two groups according to the value of j =
|l + s| =
l ±
, with a maximum
number 2j + 1 of electrons in each (total (2l + 2) + 2l =
2(2l + 1) as before), and L and S cease to be
useful.
Electron configurations of the
elements Ground states of free neutral atoms
|
Element
|
K |
L |
M |
N |
O |
Lowest state |
|
1s |
2s |
2p |
3s |
3p |
3d |
4s |
4p |
4d |
4f |
5s |
5p |
5d |
5f |
5g |
|
|
|
1. |
H .
. . . |
1 |
|
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2S1/2 |
|
| 2. |
He . .
. . |
2 |
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1S0 |
| |
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| 3. |
Li .
. . . |
2 |
1 |
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2S1/2 |
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| 4. |
Be . .
. . |
2 |
2 |
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1S0 |
| 5. |
B .
. . . |
2 |
2 |
1 |
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2P1/2 |
|
| 6. |
C .
. . . |
2 |
2 |
2 |
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3P0 |
| 7. |
N .
. . . |
2 |
2 |
3 |
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4S3/2 |
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| 8. |
O .
. . . |
2 |
2 |
4 |
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3P2 |
| 9. |
F .
. . . |
2 |
2 |
5 |
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2P3/2 |
|
| 10. |
Ne . .
. . |
2 |
2 |
6 |
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1S0 |
| |
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| 11. |
Na . .
. . |
2 |
2 |
6 |
1 |
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2S1/2 |
|
| 12. |
Mg . .
. . |
2 |
2 |
6 |
2 |
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1S0 |
| 13. |
Al .
. . . |
2 |
2 |
6 |
2 |
1 |
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2P1/2 |
|
| 14. |
Si .
. . . |
2 |
2 |
6 |
2 |
2 |
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3P0 |
| 15. |
P .
. . . |
2 |
2 |
6 |
2 |
3 |
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4S3/2 |
|
| 16. |
S .
. . . |
2 |
2 |
6 |
2 |
4 |
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3P2 |
| 17. |
Cl .
. . . |
2 |
2 |
6 |
2 |
5 |
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2P3/2 |
|
| 18. |
Ar .
. . . |
2 |
2 |
6 |
2 |
6 |
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1S0 |
| |
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| 19. |
K .
. . . |
2 |
2 |
6 |
2 |
6 |
|
1 |
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|
2S1/2 |
|
| 20. |
Ca . .
. . |
2 |
2 |
6 |
2 |
6 |
|
2 |
|
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|
1S0 |
| 21. |
Sc . .
. . |
2 |
2 |
6 |
2 |
6 |
1 |
2 |
|
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|
2D3/2 |
|
| 22. |
Ti .
. . . |
2 |
2 |
6 |
2 |
6 |
2 |
2 |
|
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3F2 |
| 23. |
V .
. . . |
2 |
2 |
6 |
2 |
6 |
3 |
2 |
|
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|
4F3/2 |
|
| 24. |
Cr . .
. . |
2 |
2 |
6 |
2 |
6 |
5 |
1 |
|
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7S3 |
| 25. |
Mn . .
. . |
2 |
2 |
6 |
2 |
6 |
5 |
2 |
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6S5/2 |
|
| 26. |
Fe . .
. . |
2 |
2 |
6 |
2 |
6 |
6 |
2 |
|
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5D4 |
| 27. |
Co . .
. . |
2 |
2 |
6 |
2 |
6 |
7 |
2 |
|
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|
4F9/2 |
|
| 28. |
Ni . .
. . |
2 |
2 |
6 |
2 |
6 |
8 |
2 |
|
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3F4 |
| |
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| 29. |
Cu . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
1 |
|
|
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|
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|
2S1/2 |
|
| 30. |
Zn . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
|
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|
1S0 |
| 31. |
Ga . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
1 |
|
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|
2P1/2 |
|
| 32. |
Ge . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
2 |
|
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|
3P0 |
| 33. |
As . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
3 |
|
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|
4S3/2 |
|
| 34. |
Se . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
4 |
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|
3P2 |
| 35. |
Br . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
5 |
|
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|
2P3/2 |
|
| 36. |
Kr . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
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1S0 |
| |
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37. |
Rb . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
|
|
1 |
|
|
|
|
2S1/2 |
|
|
38. |
Sr . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
|
|
2 |
|
|
|
|
|
1S0 |
|
39. |
Y .
. . . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
1 |
|
2 |
|
|
|
|
2D3/2 |
|
|
40. |
Zr . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
2 |
|
2 |
|
|
|
|
|
3F2 |
|
41. |
Nb . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
4 |
|
1 |
|
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|
6D1/2 |
|
|
42. |
Mo . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
5 |
|
1 |
|
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|
7S 3 |
|
43. |
Tc . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
5 |
|
2 |
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|
6S5/2 |
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|
44. |
Ru . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
7 |
|
1 |
|
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|
5F5 |
|
45. |
Rh . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
8 |
|
1 |
|
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|
4F9/2 |
|
|
46. |
Pd . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
10 |
|
|
|
|
|
|
|
1S 0 |
|
47. |
Ag . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
10 |
|
1 |
|
|
|
|
2S1/2 |
|
|
48. |
Cd . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
10 |
|
2 |
|
|
|
|
|
1S 0 |
|
49. |
In . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
10 |
|
2 |
1 |
|
|
|
2P1/2 |
|
|
50. |
Sn . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
10 |
|
2 |
2 |
|
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|
3P 0 |
|
51. |
Sb . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
10 |
|
2 |
3 |
|
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|
4S3/2 |
|
|
52. |
Te . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
10 |
|
2 |
4 |
|
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3P2 |
|
53. |
I .
. . . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
10 |
|
2 |
5 |
|
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|
2P3/2 |
|
|
54. |
Xe . .
. . |
2 |
2 |
6 |
2 |
6 |
10 |
2 |
6 |
10 |
|
2 |
6 |
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1S0 |
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2 |
8 |
18 |
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|
Element
|
K |
L |
M |
N |
O |
P |
Q |
|
|
|
|
4s |
4p |
4d |
4f |
5s |
5p |
5d |
5f |
5g |
6s |
6p |
6d |
6f |
6g |
6h |
7s |
|
55. |
Cs . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
|
2 |
6 |
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1 |
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56. |
Ba . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
|
2 |
6 |
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2 |
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57. |
La . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
|
2 |
6 |
1 |
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2 |
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58. |
Ce . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
2 |
2 |
6 |
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2 |
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59. |
Pr . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
3 |
2 |
6 |
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2 |
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60. |
Nd . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
4 |
2 |
6 |
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2 |
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61. |
Pm . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
5 |
2 |
6 |
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2 |
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62. |
Sm . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
6 |
2 |
6 |
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2 |
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63. |
Eu . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
7 |
2 |
6 |
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2 |
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64. |
Gd . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
7 |
2 |
6 |
1 |
|
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2 |
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65. |
Tb . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
9 |
2 |
6 |
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2 |
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66. |
Dy . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
10 |
2 |
6 |
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2 |
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67. |
Ho . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
11 |
2 |
6 |
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2 |
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68. |
Er . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
12 |
2 |
6 |
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2 |
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69. |
Tm . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
13 |
2 |
6 |
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2 |
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70. |
Yb . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
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2 |
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71. |
Lu . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
1 |
|
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2 |
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|
72. |
Hf . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
2 |
|
|
2 |
|
|
|
|
|
|
|
73. |
Ta . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
3 |
|
|
2 |
|
|
|
|
|
|
|
74. |
W . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
4 |
|
|
2 |
|
|
|
|
|
|
|
75. |
Re . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
5 |
|
|
2 |
|
|
|
|
|
|
|
76. |
Os . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
6 |
|
|
2 |
|
|
|
|
|
|
|
77. |
Ir . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
7 |
|
|
2 |
|
|
|
|
|
|
|
78. |
Pt . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
9 |
|
|
1 |
|
|
|
|
|
|
|
79. |
Au . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
|
|
1 |
|
|
|
|
|
|
|
80. |
Hg . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
|
|
2 |
|
|
|
|
|
|
|
81. |
Tl . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
|
|
2 |
1 |
|
|
|
|
|
|
82. |
Pb . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
|
|
2 |
2 |
|
|
|
|
|
|
83. |
Bi . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
|
|
2 |
3 |
|
|
|
|
|
|
84. |
Po . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
|
|
2 |
4 |
|
|
|
|
|
|
85. |
At . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
|
|
2 |
5 |
|
|
|
|
|
|
86. |
Em . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
|
|
2 |
6 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
87. |
Fr . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
|
|
2 |
6 |
|
|
|
|
1 |
|
88. |
Ra . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
|
|
2 |
6 |
|
|
|
|
2 |
|
89. |
Ac . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
|
|
2 |
6 |
1 |
|
|
|
2 |
|
90. |
Th . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
|
|
2 |
6 |
2 |
|
|
|
2 |
|
91. |
Pa . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
2 |
|
2 |
6 |
1 |
|
|
|
2 |
|
92. |
U . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
3 |
|
2 |
6 |
1 |
|
|
|
2 |
|
93. |
Np . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
4 |
|
2 |
6 |
1 |
|
|
|
2 |
|
94. |
Pu . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
6 |
|
2 |
6 |
|
|
|
|
2 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
95. |
Am . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
7 |
|
2 |
6 |
|
|
|
|
2 |
|
96. |
Cm . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
7 |
|
2 |
6 |
1 |
|
|
|
2 |
|
97. |
Bk . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
9 |
|
2 |
6 |
|
|
|
|
2 |
|
98. |
Cf . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
10 |
|
2 |
6 |
|
|
|
|
2 |
|
99. |
Es . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
11 |
|
2 |
6 |
|
|
|
|
2 |
|
100. |
Fm . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
12 |
|
2 |
6 |
|
|
|
|
2 |
|
101. |
Md . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
13 |
|
2 |
6 |
|
|
|
|
2 |
|
102. |
No . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
14 |
|
2 |
6 |
|
|
|
|
2 |
|
103. |
Lr . .
. . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
14 |
|
2 |
6 |
1 |
|
|
|
2 |
|
104. |
* .
. . . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
14 |
|
2 |
6 |
2 |
|
|
|
2 |
|
105. |
* .
. . . |
2 |
8 |
18 |
2 |
6 |
10 |
14 |
2 |
6 |
10 |
14 |
|
2 |
6 |
3 |
|
|
|
2 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* See footnote to Table of the Elements (section 3.1.2 footnotes)
for nomenclature.
J.C. Rivière/M.P. Seah
|