2.6: Slater's Rules - Chemistry LibreTexts https://chem.libretexts.org/LibreTexts/Mount_Royal_University/Chem_...

2.6: SLATER'S RULES

We have previously described the concepts of electron shielding, orbital penetration and effective nuclear charge, but we did so
in a qualitative manner. In this section, we explore one model for quantitatively estimating the impact of electron shielding, and
then use that to calculate the effective nuclear charge experienced by an electron in an atom. The model we will use is known as
Slater's Rules (J.C. Slater, Phys Rev 1930, 36, 57).

SLATER'S RULES
The general principle behind Slater's Rule is that the actual charge felt by an electron is equal to what you'd expect the charge to
be from a certain number of protons, but minus a certain amount of charge from other electrons. Slater's rules allow you to
estimate the effective nuclear charge  from the real number of protons in the nucleus and the effective shielding of electrons
in each orbital "shell" (e.g., to compare the effective nuclear charge and shielding 3d and 4s in transition metals). Slater's rules
are fairly simple and produce fairly accurate predictions of things like the electron configurations and ionization energies.

These rules are summarized in Figure and Table .

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Figure : Graphical depiction of Slater's rules with shielding constants indicated.

Shielding happens when electrons in lower valence shells (or the same valence shell) provide a repulsive force to valence
electrons, thereby "negating" some of the attractive force from the positive nucleus. Electrons really close to the atom (n-2 or
lower) pretty much just look like protons, so they completely negate. As electrons get closer to the electron of interest, some
more complex interactions happen that reduce this shielding. T

Electrons in
group(s) with
Electrons in Electrons in all
principal
Other electrons group(s) with group(s) with
quantum
Group in the same principal principal
number n and
group quantum quantum
azimuthal
number n-1 number < n-1
quantum
number < l

[1s] 0.30 - - -

[ns,np] 0.35 - 0.85 1

[nd] or [nf] 0.35 1 1 1

The shielding numbers in Table were derived semi-empirically (i.e., derived from experiments) as opposed to theoretical
calculations. This is because quantum mechanics makes calculating shielding effects quite difficult, which is outside the scope
of this Module.

CALCULATING S
Sum together the contributions as described in the appropriate rule above to obtain an estimate of the shielding constant, S,
which is found by totaling the screening by all electrons except the one in question.

where

is the number of electrons in a specific shell and subshell and

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is the shielding of the electrions subject to Slater's rules

CALCULATING ZEFF
One set of estimates for the effective nuclear charge ( ) was presented in Figure 2.5.1. Previously, we described as being

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less than the actual nuclear charge ( ) because of the repulsive interaction between core and valence electrons. We can
quantitatively represent this difference between and as follows:

Rearranging this formula to solve for we obtain:

We can then substitute the shielding constant   obtained using Equation to calculate an estimate of   for the
corresponding atomic electron.

SUMMARY
Slater's Rules can be used as a model of shielding. This permits us to quantify both the amount of shielding experienced by an
electron and the resulting effective nuclear charge. Others performed better optimizations of using variational Hartree-
Fock methods. For example, Clementi and Raimondi published "Atomic Screening Constants from SCF Functions." J Chem
Phys (1963) 38, 2686–2689.

REFERENCES
James L. Reed, "The Genius of Slater's Rules" , J. Chem. Educ., 1999, 76 (6), p 802

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David Tudela, "Slater's rules and electron configurations", J. Chem. Educ., 1993, 70 (11), p 956
Kimberley A. Waldron, Erin M. Fehringer, Amy E. Streeb, Jennifer E. Trosky and Joshua J. Pearson, "Screening Percentages
Based on Slater Effective Nuclear Charge as a Versatile Tool for Teaching Periodic Trends", J. Chem. Educ., 2001, 78 (5), p
635

CONTRIBUTORS
Brett McCollum (Mount Royal University)

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