Jorge Medina

ENG 363
Dr. Bruce

Effective Nuclear Charge

The attraction between an electron and the positively charged nucleus of its atom, considering any

“blocking” or shielding of the nucleus’ charge by any other electrons closer to the nucleus.

Effective nuclear charge approximates the pull of the nucleus on an electron of a multielectron atom

taking into account that some electrons are, on average, closer to the nucleus. Like fans at a crowded

concert, these closer electrons block (or shield) ones farther away from the full effect of the nucleus,

effectively cancelling some of its pull (see figure 1). This difference between actual “unblocked” nuclear

charge and effective nuclear charge helps us explain many atomic properties like atomic radius or

ionization energy, which play a role in chemical reactivity. [6, 9]

Figure 1: A graphical explanation of effective nuclear charge. From [12]. No author. Used under Creative Commons CC0 1.0

Universal Public Domain Dedication.

1. The Structure of Atoms and Electron Configurations

Our best current model of the atom tells us that unlike what is commonly believed, electrons do not

move in fixed orbits around the nucleus. Instead, we can only speak of places where an electron is most

likely to be. These places are called orbitals.

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ENG 363
Dr. Bruce

Just like a house has an address with a house number, city, and state, the places where electrons

can be are described by several different numbers, each of which tells us something about how the

orbital “looks”: The principal number (n) tells us the orbital’s size, while the angular momentum

quantum number (l) tells us the orbital’s shape. Orbital shapes are also referred to by the letters s, p, d

and f, with each letter representing a different value of the angular number l.

For example, a 1s orbital (n = 1, l = 0) is a small sphere with the nucleus at the center:

Figure 2: Probability plot for the 1s orbital of the hydrogen atom. Each blue dot represents a probable electron location. [3]

A 2s orbital (n = 2, l = 0) is a slightly bigger sphere, since it has a larger size number n and the same

shape number l:

Figure 3: Probability plot for the 2s orbital of the hydrogen atom. [3]

Finally, a 2p (n = 2, l = 1) orbital is a of the same general size as the 2s but hourglass-shaped

instead of spherical, since it has the same size number n, but a different shape number l:

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ENG 363
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Figure 4: Probability plot for the 2p orbital of the hydrogen atom. [3]

In atoms with multiple electrons several orbitals must be filled, and orbitals that are on average

closer to the nucleus are filled first. For example, an atom of boron has 5 electrons, and its electron

filling configuration is:

B: 1s2 2s2 2p1.

The 1s orbital is filled first (with 2 electrons) because it is the smallest one, and therefore the closest

one to the nucleus. The 2s orbital is filled before the 2p orbital because of its shape, as electrons are

more likely to be closer to the nucleus in the spherical s orbitals than they are in the hourglass-shaped p

orbitals.

2. Shielding and Penetration

Because orbitals come in different shapes and sizes, both an electron’s ability to be near the nucleus

(its penetration) and its ability to block other electrons from the effects of the nucleus (its shielding)

depend on the kind of orbital the electron is in. The difference between the actual charge of a nucleus

and the effective nuclear charge experienced by an electron depends both on the electron’s own

penetration and on the amount of shielding caused by other electrons. In the case of boron, if we

compare one of the 2s electrons to the 2p electron, we expect the 2s electron to experience a higher

effective nuclear charge, since 2s electrons have more penetration and 2p electrons are less effective at

shielding. In calculating effective nuclear charge, the best formulas are those that fit this expectation

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ENG 363
Dr. Bruce

3. Calculating Effective Nuclear Charge.

In general, effective nuclear charge is found using the formula:

Zeff = Z – S.

Where Zeff is the effective nuclear charge, Z is the atomic number and S is the shielding constant. Zeff

is assumed to be unitless since we are only interested in its magnitude as it compares to the charge of

an electron (-1) or a proton (+1). There are three main ways of calculating the value of S, each both

more complicated and more accurate than the last:

• The core electron method, which doesn’t account for shielding or penetration differences [8]

• Slater’s method, which only accounts for shielding differences [7, 10]

• Clementi’s method, which accounts for both shielding and penetration. [2, 4]

Because we already know what to expect, we will use boron (atomic number 5) to demonstrate the

simplest method

a. Using only core electrons [8]: This is the simplest method, but it also assumes all orbitals shield

and penetrate in the same way, regardless of their shape or size. This incorrectly results in the

same effective nuclear charge value for both 2s and 2p electrons. To calculate S:

1. Write down the electron configuration of the atom:

B: 1s2 2s2 2p1

2. Choose an electron of interest and write down the value of its size number (n):

For any 2s or 2p electron n = 2

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Jorge Medina
ENG 363
Dr. Bruce

3. Any electron with a lower n value than the one for the chosen electron contributes 1 unit to

S:

There are 2 total electrons with n = 1, so S = 2

4. Any electron with an equal or greater n value than the one for the chosen electron

contributes nothing to S:

There are 3 total electrons with n = 2, so none of them contribute

Using this method, the shielding constant S for both 2s and 2p electrons in boron would be S =

2, and the effective nuclear charge then would be:

Zeff = 5 – 2 = 3

4. Effective Nuclear Charge, Periodic Trends and Reactivity.

The trend in effective nuclear charge across the periodic table looks like this:

Figure 5: Effective nuclear charge vs. atomic number [1]

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ENG 363
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This trend broadly repeats itself in many other atomic properties, including atomic/ionic size

and ionization energy (the energy required to take an electron away from an atom):

Figure 6: Atomic radius vs. atomic number [7]

Figure 7: First ionization energy vs. atomic number [7]

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ENG 363
Dr. Bruce

The variations in both properties can be explained by thinking of effective nuclear charge as a

measure of how tightly electrons are bound to the nucleus. More tightly bound electrons are both closer

to the nucleus and harder to remove resulting in smaller radii and higher ionization energies. Both size

and ionization are a crucial factors in things ranging from the relative acidity of different organic

compounds [5, 11] to the strength of materials [9], to their electrical conductivity [6]

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ENG 363
Dr. Bruce

References

1. Atkins, P.W. and L. Jones, Chemical principles : the quest for insight. 4th ed. 2008, New York:
W.H. Freeman. xxv, 787 p.
2. Clementi, E.t. and D.-L. Raimondi, Atomic screening constants from SCF functions. The Journal of
Chemical Physics, 1963. 38(11): p. 2686-2689.
3. Fernandez, C.R. and A. Santos. Plots of quantum probability density functions in the hydrogen
atom. 2012, April 12 September 23, 2020]; Available
from: http://demonstrations.wolfram.com/PlotsOfQuantumProbabilityDensityFunctionsInTheH
ydrogenAtom/.
4. Huheey, J.E., Inorganic chemistry; principles of structure and reactivity. 1972, New York,: Harper
& Row. xvi, 737 p.
5. Klein, D.R., Organic chemistry. Second edition. ed. 2015, Hoboken, NJ: Wiley. xxii, 1278 pages.
6. Liang, Z., et al., Influence of dopant size and electron affinity on the electrical conductivity and
thermoelectric properties of a series of conjugated polymers. Journal of Materials Chemistry A,
2018. 6(34): p. 16495-16505.
7. Oxtoby, D.W., H.P. Gillis, and A. Campion, Principles of modern chemistry. 7th ed. 2012,
Belmont, Calif.: Brooks/Cole Cengage Learning.
8. Petrucci, R.H., W.S. Harwood, and F.G. Herring, General chemistry : principles and modern
applications. 8th ed. 2002, Upper Saddle River, N.J.: Prentice Hall.
9. Schweinfest, R., A.T. Paxton, and M.W. Finnis, Bismuth embrittlement of copper is an atomic size
effect. Nature, 2004. 432(7020): p. 1008-1011.
10. Slater, J.C., Atomic Shielding Constants. Physical Review, 1930. 36: p. 57-64.
11. Wade, L.G., Organic chemistry. 8th ed. 2013, Boston: Pearson. xxxvi, 1258 p.
12. Wikipedia, c. Effective nuclear charge. 13 September 2020 16:17 UTC 28 September 2020 23:52
UTC]; Available from:
https://en.wikipedia.org/w/index.php?title=Effective_nuclear_charge&oldid=978216438.