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In the Classroom

Screening Percentages Based on Slater Effective Nuclear


Charge as a Versatile Tool for Teaching Periodic Trends
Kimberley A. Waldron,* Erin M. Fehringer, Amy E. Streeb, Jennifer E. Trosky, and Joshua J. Pearson
Department of Chemistry, Regis University, Denver, CO 80221; *kwaldron@regis.edu

Background technique such as the Hartree–Fock calculation (4 ), which


is also a variational method. However, as an empirical method
The solutions to the Schrödinger equation allow us to based on ionization energies, Slater’s rules have proven useful
understand the hydrogen atom in terms of its electron den- for predicting trends such as those for electronegativity and
sity at radial distances from the nucleus. Consideration of ionic radius, and Slater’s optimized values of Z * and n*
the helium atom brings new complications. Each of helium’s should be useful for predicting ionization energies (in units
two electrons does not each “feel” two full units of nuclear of electron volts) according to the following equation (5):
charge owing to the presence of the other electron. The inter-
E/eV = (Z *)2(13.6 eV)/(n*)2 (3)
electronic interaction between its two electrons must be esti-
mated. One of the most common ways to approach this Comparison with actual ionization energy data shows that
problem is to assume that each electron in a given atom is the correlation is a rough one. In addition, Slater’s Z * values
hydrogen-like and that it experiences interactions due to the are a limited pedagogical tool for understanding shielding
presence of other electrons. This can be accomplished using the trends throughout the periodic table, as we shall see.
“variational method” in which an energy is arbitrarily set for
the system and that energy is minimized by the manipulation Improving the Pedagogical Value of Slater’s Rules
of several parameters incorporated in the orbital wave functions.
J. C. Slater adopted this type of approach by developing At several points during an undergraduate curriculum
“Slater-type orbitals” (STOs), which approximate hydrogen- in chemistry, students are exposed to periodic trends in atomic
like orbitals. These (nodeless) orbitals are expressed by Slater size and electronegativity. For introductory students this
in terms of a wave function with polar coordinates (1, 2): information is presented in a format that depicts the periodic
table and indicates the “corners” of the table that represent
ψ (r,θ, φ) = Nnl r n᎑1e᎑ξr Yml (θ, φ) (1)
maxima and minima in the specific trend. Often, a simplified
where Y are the spherical harmonics and ξ = Z*/n*. Using “screening constant” is introduced. This is easily calculated by
the variational method, the “effective” principal quantum assigning a value of 1.0 to each core electron and subtracting
number n* and the “effective” atomic number Z * are varied this value from the total number of positive charges in the
by Slater in a way that minimizes the energy of the system. nucleus. This method assumes complete shielding by all core
In order to obtain the best value of ξ , Slater developed a set of electrons and ignores interelectronic interactions within the
rules that allows quantification of shielding by partitioning valence shell. For more advanced students, horizontal periodic
the electrons into groups: electrons within the same group trends often are explained using Slater’s rules and the notion
or occupying “inner” groups all contribute to the shielding of effective nuclear charge, Z *.
(3). For example, rule four provides that an electron in a shell The results of applying Slater’s rules illustrate their peda-
directly below the electron in question will “shield” that gogical usefulness for the 2p subshell elements, as shown in
electron by 85%. Summation of shielding contributions from Figure 1A. The larger value of Z * can be correlated to an
all electrons lying below the electron in question provides the increase in electronegativity and to a decrease in atomic size
total shielding, S, which is then used to calculate the effec- owing to the increased “pull” by the nucleus. However, Slater’s
tive nuclear charge, Z *: rules lose their pedagogical usefulness when applied to vertical
trends on the periodic table. For example, the alkali metals
Z* = Z – S (2)
have Z * values as shown in Figure 1B. The lack of a trend in
Slater’s rules provide only approximate values for electron this series of elements, and in all groups across the table, is a
energies in polyatomic atoms partly because they ignore the tradeoff between an increasing value of n (decreases Z *) and
presence of nodes. Certainly, it is possible to obtain more increasing numbers of protons in the nucleus (increases Z *).
precise estimates using a more sophisticated computational Therefore, while horizontal trends mirror trends in electro-
negativity and atomic radius, vertical trends do not. Using
Slater’s rules, the periodic table is made up of a series of Z *
values that are limited in range and function.
Li Be B C N O F Ne
A
1.30 1.95 2.60 3.25 3.90 4.55 5.20 5.85
Screening Percentages
H Li Na K Rb Cs A more nearly ideal method for predicting effective nuclear
B 1.0 1.3 2.2 2.2 2.2 2.2 charge would provide a vertical trend that accounts for in-
creases in atomic and ionic radii, decreases in first ionization
Figure 1. Slater Z* values for the (A) n = 2 elements and (B) group energies, and decreases in electronegativities. A novel method
1A elements. for expressing effective nuclear charge makes use of a “screening

JChemEd.chem.wisc.edu • Vol. 78 No. 5 May 2001 • Journal of Chemical Education 635


In the Classroom

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

Figure 2. Periodic table with 11 12 13 14 15 16 17 18


element shading proportional to Na Mg Al Si P S Cl Ar
the screening percentage, SP.
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

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

636 Journal of Chemical Education • Vol. 78 No. 5 May 2001 • JChemEd.chem.wisc.edu


In the Classroom

size of germanium, which sterically restricts the allowable 98 0.196

number of oxo groups, in comparison with the larger tin atom,

Reciprocal Ionization Energy / eV ᎑1


which can fit six such ligands into its coordination sphere. 96
0.186
For experienced students with previous course work in

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

JChemEd.chem.wisc.edu • Vol. 78 No. 5 May 2001 • Journal of Chemical Education 637


In the Classroom

In the case of arsenic, for example, Figure 3 shows that 0.20


the screening percentage, SP, is 70.3%. This can be used to

Reciprocal Ionization Energy / eV ᎑1


calculate Z * as follows:
Z * = (100 – SP)/100% × Z = 100

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

(9.80) /(4 × 2.94) × 13.6 eV = 9.44 eV


2 2

The reported value is 9.814 eV. 25 0.00


The precision of this calculation depends on the value Be Mg Ca Sr Ba

of q, which in turn depends on the number of elements in a


group that is assigned a value of q in Figure 5. For most
elements, the predicted IE value will fall within ±1.5 eV of
1.4
the experimental value. However, some elements do not fall
in this range. Nevertheless, trends in IE values are maintained
1.2
with this prediction method. A plot of predicted and experi- 100

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

200 Covalent Radius / pm


11

60
10 150

9
40
100
IE / eV

7 20 50
Be Mg Ca Sr Ba

6
Group 2 Element

5 Figure 7. Top: Screening percentage [䊏] correlated with the recipro-


Be Mg Ca Sr Ba
cal of the ionization energy (IE/eV)᎑1- [䊉] for the group 2 elements.
Group 2 Element Middle: Screening percentage [䊏] correlated with the reciprocal of
the electronegativity [䊉] for the group 2 elements. Bottom: Screening
Figure 6. Comparison of (dotted line) predicted and (solid line) percentage [䊏] correlated with the covalent radius/pm [䊉] for the
experimental ionization energies for the group 2 elements. group 2 elements.

638 Journal of Chemical Education • Vol. 78 No. 5 May 2001 • JChemEd.chem.wisc.edu


In the Classroom

It is evident that even though the predicted IE value for Note


nitrogen does not fall within the 1.5 eV range, the trend is
1. Note that for s and p electron calculations, f electrons will
retained in the series of predicted values.
usually be in the (n – 2) shell.
A more important consideration is the inverse correlation
between ionization energies and the newly defined screening
percentage. Figure 7 shows a plot of SP versus the reciprocal Literature Cited
of the experimental IE values for the group 2 elements. As
1. Coulson, C. A. Valence, 2nd ed.; Oxford University Press:
the plot shows, the notion of screening percentage should be
London, 1961; p 29.
useful in demonstrating trends in ionization energies. The
2. Slater, J. C. Quantum Theory of Atomic Structure, Vol. 1;
figure also shows the inverse correlation between screening
McGraw Hill: York, PA, 1960; p 112.
percentages and Allred–Rochow electronegativities (7), as well
3. Adapted from Porterfield, W. W. Inorganic Chemistry: A Uni-
as the direct correlation with covalent radii (8). This clear
fied Approach; Academic: New York, 1993; p 23. The shield-
correlation will be a practical way for students to understand
ing constant, S, is determined by dividing the electrons into
shielding as it relates directly to changes in IE, as well as to
the following groups, each having a different shielding con-
trends in electronegativity and atomic size. Clearly, all these
stant: 1s; 2s, 2p; 3s, 3p; 3d. That is, the s and p of a given n
trends can ultimately be explained in terms of “pull” on valence
are grouped together, but the d and f are separated. The shield-
electrons by the nuclear charge. Screening percentages present
ing constant, S is formed for any group of electrons from the
a simple way to illustrate this. This new concept should provide
following contributions: (rule 1) electrons from any shell out-
a very useful pedagogical tool whether used qualitatively or
side the one considered contribute 0.0 to the screening; (rule
quantitatively.
2) an amount 0.35 is counted for each other electron in the
group considered except in the 1s group, where 0.30 is used
Conclusions
instead; (rule 3) if the electron considered is a d or f electron,
A periodic table that depicts all values of valence electron each electron in an inner group contributes 1.00 to the screen-
screening percentages can be used for teaching various facets ing (it screens completely); (rule 4) if the electron considered
of electronic structure to students at all levels. Figure 2 depicts is an s or p electron, an amount 0.85 is counted for each elec-
a periodic table that is shaded in proportion to screening tron with quantum number of n – 1 and 1.00 from each elec-
percentages. It can be used in the most introductory courses tron still further in.
to introduce the notion that valence electrons do not “feel” 4. Fock, V. Z. Physik 1930, 61, 126.
the full force of the nucleus because of the presence of other 5. Slater, J. C. Phys. Rev. 1930, 36, 37.
electrons. More advanced students can be shown the effect of 6. Screening percentages are empirically derived from
introducing d and f electrons into an atom’s core and the real experimental ionization energy data from the following
effects of the resulting scandide and lanthanide contractions. sources: Martin, W. C.; Hogan, L.; Reader, J.; Sugar, J. J. Phys.
Trends within the 4f elements are also well represented using Chem. Ref. Data 1974, 3. Moore, C. E. Atomic Energy Levels;
screening percentages. This method permits direct comparison NBS Circular 467; National Bureau of Standards: Washing-
of ionization energy, atomic radius, and electronegativity data ton, DC, 1970.
to screening percentages. Screening percentages should prove 7. Allred, A. L.; Rochow, E.G. J. Inorg. Nucl. Chem. 1961, 17, 215.
to be an effective instrument for teaching periodic trends to 8. Sanderson, R. T. Inorganic Chemistry; Reinhold: New York,
any level of undergraduate student. 1967; p 74.

JChemEd.chem.wisc.edu • Vol. 78 No. 5 May 2001 • Journal of Chemical Education 639