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percentage” rather than a “screening constant” (6 ). The fol- Table 1. Slater Z* Values and Screening Percentages
lowing example illustrates the usefulness of this approach for Calculated with Traditional and Improved Rules
group 13. For boron, Slater’s rules give Percentage
Atomic Slater S Slater Z * Based on Improved Improved
S = (0.35 × 2) + (0.85 × 2) = 2.4 Element
No. Value Value Slater S Value a Percentage
Value
This value, subtracted from the atomic number of boron (5 – B 5 2.4 2.6 48 (2.4) 48
2.4 = 2.6) gives the effective nuclear charge, Z*. The improved
Al 13 9.5 3.5 73 (9.5) 73
method uses a percentage that gives the sum of shielding
Ga 31 26.0 5.0 84 22.5 73
divided by the atomic number:
In 49 44.0 5.0 90 40.5 83
SP = S/Z × 100% = 2.4/5.0 × 100% = 48% (4) Tl 81 76.0 5.0 94 68.2 84
This value of 48% provides a clear indicator of the percentage aImproved
values are only valid for elements with d and/or f electrons.
of the nuclear charge that is “shielded from” valence electrons Numbers in parentheses are not changed from the original Slater method.
in the 2p shell of boron. The same method gives a value of
73% for aluminum. Pedagogical Utility
The next element in the series, gallium, follows the first
series of d electrons. The result is a “scandide contraction”, which The use of screening percentages offers a simple way
gives gallium size, ionization energy, and electronegativity to teach periodic trends to beginning students of chemistry.
values similar to those of aluminum or boron. This anomaly For example, a periodic table that has elements shaded in
is not accounted for by Slater’s rules, which count each d proportion to their screening percentages could be used to
electron in the 3d series with a contribution of 0.85 to the introduce the notion of “shielding”, which is often not covered
overall shielding value. In fact, each of these d electrons shields at the introductory level. The use of such a tool, shown in
the increasing nuclear charge poorly. When gallium is Figure 2, allows students to see the importance of electron
reached, the nuclear charge has increased dramatically over shell hierarchies and the “canceling” effect of core electrons
the increased electron density from added 3d electrons. This without the need for explaining screening constants, screening
causes the “contraction” in gallium’s size. To compensate for percentages, interelectronic interaction terms, or orbital
this effect as well as the lanthanide contraction that causes a penetration.
decrease in the 5d transition metal series, Slater’s rules have For more advanced students (perhaps at the “majors”
been revised empirically as follows: introductory level), a table that lists each percentage could
be devised, as in Figure 3. This approach allows students to
Rule 4: For s and p electron calculations, (n – 1) d elec-
see the effects of screening in a quantitative way. Students
trons are counted as 0.50 each. All f electrons are counted
who have been introduced to radial distribution functions
as 0.69 each. The rules for calculating d and f electron
in combination with screening percentage data can clearly
values remain the same. That is, same-shell electrons
see the results of the scandide and lanthanide contractions.
count 0.35 and all others count 1.00.
Real similarities between the 3p/4p elements and the 4d/5d
These revised rules make each d electron a truly poor shielder elements can be demonstrated as a result of this discussion.
with a value of 50% rather than 85%. Moreover, f electrons, For example, because germanium is similar in size to silicon, it
which are poorer shielders, are valued at 69% rather than forms similar oxo ions such as SiO44᎑ and GeO44᎑, whereas tin
100%.1 The result for group 13 is shown in Table 1. forms SnO68᎑. This is at least consistent with the contracted
1 2
H He
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rh Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 57* 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Ti Pb Bi Po At Rn
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Screening Percentage
inorganic chemistry, the screening percentages illustrated in
94
Figure 3 can also be used to introduce trends in the lanthanide 0.176
elements, which are often oversimplified. For example, when
Slater’s rules are invoked, the f electrons each contribute 100% 92
to the shielding of each added nuclear charge across the lan- 0.166
thanide series. This produces no change across the lanthanides 90
when Slater Z * values are calculated. Although the differences
are small, the IE values for the lanthanide elements do increase 0.156
88
by 0.83 eV across the 4f series. The added fact that the size of
the lanthanides decreases by 11 pm across the series from ce- 0.146
rium to lutetium indicates that there must be some penetration 86
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
of 6s electron density into the 4f shell. This opposes the idea
that although 6s electrons have superior penetrating power, Lanthanide Elements
they do not penetrate (n – 2) f orbitals to an appreciable extent.
Figure 4. Screening percentage [䊉] correlated with the reciprocal
Figure 4 clearly shows that the trend in reciprocal IE values
of the ionization energy (IE/eV)᎑1 [䊏] for the lanthanide elements.
across the lanthanides is mirrored by the screening percentage
that provides for the imperfect screening ability of (n – 2) f
electrons.
The new method counts each f electron as 0.69, an em-
pirically derived value that gives the best fit with the lanthanide Correlation of Screening Percentages with Ionization
data. The empirical 0.69 value suggests that the lanthanide f Potentials
orbitals are penetrated by 6s electrons to an extent of approxi-
mately 31%. This can be demonstrated to students using Slater used empirical evidence from ionization energy
radial distribution functions. The penetrating ability of the calculations to formulate his rules for calculating Z *. The
6s electrons by virtue of their electron densities near the value n* that he designated and used, for example in eq 3, is
nucleus, however small, is manifested in the decreasing SP equal to nx, where x is a “fudge factor” required to optimize
values across the lanthanide series. Therefore, although nodes his resultant energy values. In a similar way, a fudge factor q
are not accounted for directly in this improved method (or with has been included in the following expression relating the
Slater’s method), their effect is clearly seen when a 69% value of Z * to the ionization energy (IE):
screening factor for f electrons is substituted into the calcula-
tion. The effect of the lanthanide contraction in real systems (Z*)2/(nq) 2 × 13.6 eV = IE/eV (5)
can be illustrated to advanced chemistry students using, for
example, the similarities between oxo anions formed by 4d This equation provides a loose relationship between Z * and
and 5d metals or the similarities in 4d and 5d transition metal IE that can be used to produce rough estimates of ionization
compound basicities. energy based on the new rules established in this paper.
1 2
H He
0.0 15.0
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
56.7 51.3 48.0 45.8 44.3 43.1 43.2 41.5
Figure 3. Periodic table with the 11 12 13 14 15 16 17 18
screening percentage, SP, inserted Na Mg Al Si P S Cl Ar
in place of relative atomic mass 80.0 76.2 73.1 70.4 68.0 65.9 64.1 58.6
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
for each element.
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
88.4 85.8 84.0 82.5 81.1 80.4 78.6 77.5 76.5 75.5 75.2 73.8 72.5 71.4 70.3 69.3 68.3 67.4
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rh Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
94.0 92.5 91.4 90.4 89.7 88.8 87.5 87.0 86.2 85.1 84.7 83.6 82.6 81.7 80.8 79.9 79.0 78.2
55 56 57* 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Ti Pb Bi Po At Rn
96.0 94.9 94.1 88.6 88.1 87.6 87.1 86.6 86.1 85.8 85.4 84.7 84.2 83.6 83.0 82.4 81.9 81.3
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
93.7 93.5 93.1 92.7 92.3 92.0 91.3 91.3 90.9 90.6 90.3 90.0 89.7 89.1
Screening Percentage
0.15
(100 – 70.3%)/100% × 33 = 9.80
This value can then be inserted into eq 5 and the ionization
energy can be predicted with the proper value of q. As in 75
0.10
Slater’s method, the fudge factor used in this method, q,
varies according to the element’s position on the periodic table.
The q values are compiled in Figure 5. Arsenic has a q value of
50
2.94, and so the resulting ionization energy is predicted to be 0.05
Reciprocal Electronegativity
mental IE values is shown in Figure 6 for group 2 elements. Screening Percentage 1.0
80
0.8
s block d block p block 60
elements elements elements
0.6
40
1.00 1.26
0.4
1.10 1.75 2.20
1.02 1.80 2.12 20
0.2
0.94 1.80 1.96 2.94
0.84 1.48 1.57 2.61
0 0.0
0.73 2.00 2.25 3.01 Be Mg Ca Sr Ba
f block elements
100
1.33 1.45
250
Figure 5. Periodic table divided into blocks of elements, with asso-
ciated values of q indicated (see eq 5).
Screening Percentage
80
60
10 150
9
40
100
IE / eV
7 20 50
Be Mg Ca Sr Ba
6
Group 2 Element