Calculated Effective Nuclear Charge (Z*) Values

letters Element Electron Z*(3d) Z*(4s) av

Configuration

Slater’s Rules and Electron Configurations 3.00 3.00

Sc [Ar 3d14s2 3.00
To the Editor: [Ar 3d24s1 2.65 2.50 2.60
[Ar 3d3 2.30 2.30
The article “The Use of Effective Nuclear Charge (Z)
Calculations to Illustrate the Relative Energies of ns and Ti [Ar]3d24s2 3.65 3.15 3.40
3.30 2.65 3.14
(n l)d Orbitals” by Christina Poth Brink (I) describes the
- [Ar]3d34s1
use of Slater’s rules to account for the fact that while the [Ar]3d4 2.95 2.95
4s orbital fills before the 3d orbitals for the 4th row ele-
V 4.30 3.30 3.90
ments, the 4s electrons are the first to be removed on ion- [Ar]3d34s2
3.95 2.80 3.72
ization. Slater’s rules had been used previously to justify [Ar]3d44s1
[Ar]3d5 3.60 3.60
that the ground state electron configuration for potassium
is [ArMs1 rather than [ArjSd1 (2, 3). Also, I have used a Cr [Ar]3d44s2 4.95 3.45 4.45
similar approach to that described by Brink (I) to illustr- [Ar]3d54s1 4.60 2.95 4.33
ate that the 3d orbitals become progressively more stable [Ar]3d6 4.25 4.25
than the 4s orbital on going through the first transition
Mn [Ar]3d54s2 5.60 3.60 5.03
series. At this point, students often ask why, for example, 5.25 3.10 4.94
[Ar]3d64s1
the ground state electron configuration for Ti is [Ar]3d24s2 [Ar] 3d7 4.90 4.90
rather than [Ar]3d4. However, this problem can be solved
again with the use of Slater’s rules, which lead to an effec- Fe [Ar]3d64s2 6.25 3.75 5.63
tive nuclear charge of 3.15 for 4s electrons and 3.65 for 3d [Ar]3d74s1 5.90 3.25 5.57
electrons if the electron configuration of Ti is [Ar]3d24s2 [Ar]3d8 5.55 5.55
(1). On the other hand, if the electron configuration of Ti Co 6.90 3.90 6.23
[Ar]3d74s2
had been [Ar]3d4, the effective nuclear charge that the 3d [Ar]3d84s1 6.55 3.40 6.20
electrons would have experienced is: [Ar]3d9 6.20 6.20
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{ls2)(2s22p6)(3s23p6)(3d4) Ni [Ar]3d84s2 7.55 4.05 6.85

S = (3 x (0.35)) + (18 x (1.00)) 19.05 6.84
Downloaded via 115.248.191.25 on August 16, 2019 at 09:33:49 (UTC).

=
[Ar]3d94s1 7.20 3.55
Z* = 22.00 19.05 = 2.95
-

[Ar]3d10 6.85 6.85

Consequently, despite the fact that the 3d orbitals are Cu [Ar]3d94s2 8.20 4.20 7.47
lower in energy than the 4s orbital, both 3d and 4s elec- [Ar]3d104s1 7.85 3.70 7.47
trons of Ti [Ar]3d24s2 feel a higher effective nuclear charge
and are therefore more stable than the 3d electrons of Ti number for polyelectronic atoms. This misleading diagram
[Ar]3d4. Accordingly, the ground state electron configura- showing that the orbital energy for the 4s orbital becomes
tion of Ti will be [Ar]3d24s2 rather than [Ar]3d4. Similarly, lower than for 3d orbitals for certain values of atomic num-
calculations can be performed for the effective nuclear ber is still contained in some inorganic chemistry text-
charge experienced by the 3d and 4s electrons for the pos- books published during the last decade (8-12).
sible [Ar]3dn4s2, [Ar]3dn+14s1 and [Ar]3d"+24s° electron In conclusion, despite the apparent usefulness of Slater’s
configurations of the first transition metal row elements. rules to account for the ground state electron configuration
The results are summarized in the table, where Z av is the of the 4th row elements, they lead to the erroneous idea
average of the effective nuclear charge calculated for the that for potassium the 4s orbital is lower in energy than
3d and 4s electrons. It can be seen from the table that the 3d orbital. Rather, the energy due to the [Ar]4s1 config-
while the difference between the effective nuclear charge uration is lower than that due to the [Ar]3dT configuration
experienced by the 3d and 4s electrons increases along the because of the electron repulsion term, in spite of the fact
first transition series, the average effective nuclear charge that the 4s orbital energy is higher than the 3d orbital en-
for the different possible electron configurations becomes ergy (6). Nevertheless, the simplicity of the Slater’s rules
more similar from Sc to Cu, so that exceptions to the elec- makes them useful, for teaching purposes, to discern
tron configuration [Ar]3d"4s2 are not surprising. trends along the 4th row elements.
It is important to note that the calculations reported above
and in reference (1) are useful to discern trends along the 4th Literature Cited
Brink, C. J. Chem. Educ. 1991, 68, 376-377.
row elements, but the actual numerical values must be inter-
1. P.
2. Sharpe, A. G. Inorganic Chemistry, 2nd ed.; Longman: London, 1986; Chapter 3, p 67.
preted with considerable caution. More specifically, Slater’s 3. Butler, I. S.; Harrod. J. F. Inorganic Chemistry, Benjamin-Cummings: Redwood City,
rules are based on simplifying assumptions that lead to poor CA, 1989; Chapter 2, p 55. The possible electron configurations for potassium are
misprinted as [Ar]3s23pfi3dI and [Ar|3s“3pb4s'.
agreement between the calculated and true effective nuclear 4. Huheey, J. E. Inorganic Chemistry, 3rd ed.; Harper and Row: New York, 1983; Chap-
charges (3), and, therefore, the electronic energies estimated ter 2, p 37.
5. Porterfield, W. W. Inorganic Chemistry; Addison-Wesley: Reading, MA, 1984; Chap-
by Slater’s rules are often not veiy accurate (4). In particular, ter 2, p 38.
Slater’s rules underestimate the effective nuclear charge val- 6. Pilar, F. L. J. Chem. Educ. 1978, 55, 2-6.
ues for 3d electrons (5). Furthermore, the very concept of effec- 7. Scerri, E. R. J. Chem. Educ. 1989, 66, 481-483,
8. Moeller, T. Inorganic Chemistry, A Modern Introduction', Wiley: New York, 1982;
tive nuclear charge is a crude and incomplete way of taking Chapter 3, pp 57,58.
electron-electron repulsions into account (6). Consequently, 9. Cotton, F. A.; Wilkinson, G.; Gaus, P. L. Basic Inorganic Chemistry, Wiley: New York,
1987; Chapter 2, p 46.
the use of Slater’s rides leads to the result that for potassium 10. Cotton, F. A,; Wilkinson, G. Advanced Inorganic Chemistry, 5th ed.; Wiley: New
the 4s orbital is lower in energy than the 3d orbital (i), while York, 1988; Chapter 17, p 628.
it is known that the 4s orbital energy is always above the 3d 11. Reference (3), p 34.
12. Shriver, D. F.; Atkins, P. W.; Langford, C. H. Inorganic Chemistry, Oxford University
orbital energy (6). As pointed by Pilar (6) and Scerri (7), the Press: Oxford, 1990; Chapter 1, p 23.
erroneous notion that the 4s orbital ever has a lower energy David Tudeia
than that of 3d is extended by textbooks containing a diagram Universidad Autonoma de Madrid
that represents the energy of atomic orbitals versus atomic 28049-Madrid (SPAIN)

956 Journal of Chemical Education