32 Chapter 2 | Atomic Structure

FIGURE 2.10 Energy Level 5g

Splitting and Overlap. 5f
4f
The differences between n=5 5d
the upper levels are
5p
exaggerated for easier 4d
visualization. This diagram n=4 5s
provides unambiguous electron 4p
configurations for elements 3d
hydrogen to vanadium. 4s

n=3 3p

3s

2p

n=2

2s

n=1 1s

b. Each electron in n – 1 groups contribute 0.85 to S.

Example: For the 3s electron of sodium, there are eight electrons in the (2s, 2p)
group. Each of these electrons contributes 0.85 to the value of S, a total contribu-
tion of 8 * 0.85 = 6.80.
c. Each electron in n – 2 or lower groups contributes 1.00 to S.
4. For nd and nf valence electrons:
a. Each electron in the same group contributes 0.35 to the value of S for each other
electron in the group. (Same rule as 3a.)
b. Each electron in groups to the left contributes 1.00 to S.
These rules are used to calculate the shielding constant S for valence electrons.
Subtracting S from the total nuclear charge Z gives the effective nuclear charge Z* on the
selected electron:
Z* = Z - S
Calculations of S and Z* follow.
EXAMPLE 2.3

Oxygen
Use Slater’s rules to calculate the shielding constant and effective nuclear charge of
a 2p electron.
Rule 1: The electron configuration is written using Slater’s groupings, in order:
(1s 2)(2s 2, 2p 4)
To calculate S for a valence 2p electron:
Rule 3a: Each other electron in the (2s 2, 2p 4) group contributes 0.35 to S.
Total contribution = 5 * 0.35 = 1.75
Rule 3b: Each 1s electron contributes 0.85 to S.
Total contribution = 2 * 0.85 = 1.70
 2.2 The Schrödinger Equation | 33

Total S = 1.75 + 1.70 = 3.45

Effective nuclear charge Z* = 8 - 3.45 = 4.55
So rather than feeling the full +8 nuclear charge, a 2p electron is calculated to
feel a charge of +4.55, or about 57% of the full nuclear charge.
Nickel
Use Slater’s rules to calculate the shielding constant and effective nuclear charge of a
3d and 4s electron.
Rule 1: The electron configuration is written (1s 2)(2s 2, 2p 6)(3s 2, 3p 6)(3d 8)(4s 2)

For a 3d electron:
Rule 4a: Each other electron in the (3d 8) group contributes 0.35 to S.
Total contribution = 7 * 0.35 = 2.45
Rule 4b: Each electron in groups to the left of (3d 8) contributes 1.00 to S.
Total contribution = 18 * 1.00 = 18.00
Total S = 2.45 + 18.00 = 20.45
Effective nuclear charge Z* = 28 - 20.45 = 7.55
For a 4s electron:
Rule 3a: The other electron in the (4s 2) group contributes 0.35 to S.
Rule 3b: Each electron in the (3s 2, 3p 6)(3d 8) groups (n – 1) contributes 0.85.
Total contribution = 16 * 0.85 = 13.60
Rule 3c: Each other electron to the left contributes 1.00. Total contribution =
10 * 1.00 = 10.00
Total S = 0.35 + 13.60 + 10.00 = 23.95
Effective nuclear charge Z * = 28 - 23.95 = 4.05
The effective nuclear charge for the 4s electron is considerably smaller than the value
for the 3d electron. This is equivalent to stating that the 4s electron is held less tightly
than the 3d and should therefore be the first removed in ionization. This is consistent
with experimental observations on nickel compounds. Ni2 + , the most common oxida-
tion state of nickel, has a configuration of [Ar] 3d8, rather than [Ar] 3d6 4s2, corre-
sponding to loss of the 4s electrons from nickel atoms. All the transition metal atoms
follow this same pattern of losing ns electrons more readily than (n – 1)d electrons.
EXERCISE 2.6 Calculate the effective nuclear charge on a 5s, 5p, and 4d electron in a
tin atom.
EXERCISE 2.7 Calculate the effective nuclear charge on a 7s, 5f, and 6d electron in a
uranium atom.
Justification for Slater’s rules comes from the electron probability curves for the orbit-
als; Slater devised these rules semiempirically using equations modeled after wavefunc-
tion equations to fit experimental data for atoms. Slater’s approach results in rules that
provide useful approximations for the effective nuclear charge an electron in an atom
actually experiences after shielding is taken into account. The s and p orbitals have
higher probabilities near the nucleus than do d orbitals of the same n, as shown earlier in
Figure 2.7. Therefore, the shielding of 3d electrons by (3s, 3p) electrons is calculated as
100% effective, a contribution of 1.00. At the same time, shielding of 3s or 3p electrons by
(2s, 2p) electrons is estimated as 85% effective, a contribution of 0.85, because the 3s and
3p orbitals have regions of significant probability close to the nucleus. Therefore, electrons
in these orbitals are not completely shielded by (2s, 2p) electrons.