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.

To talk about atoms and their properties, we must consider the interactions between electrons and

their positively charged nuclei. In atoms like H or He+ which only have one electron, we only need to

think about one of these interactions. Each “extra” electron introduced greatly increases the number of

interactions we need to consider. Because of this, any equation predicting the properties of atoms with

more than one electron can only be an approximation. [3, 7]

Effective nuclear charge is one of these approximations. It tries to account for the fact 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. [5, 8]

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

To understand how effective nuclear charge is calculated, we first need to understand how electrons

are distributed inside atoms. 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.

Just like a house has an address with a house number, city, and state, every orbital is 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.

For example, a 1s orbital 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. [11]

A 2s orbital 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. [11]
 Finally, a 2p 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:

Figure 4: Probability plot for the 2p orbital of the hydrogen atom. [11]

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 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

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.

There are several different ways of calculating the value of S, each being both increasingly difficult and

increasingly accurate. Because we already know what to expect, we will use boron (atomic number 5) to

demonstrate.

a. Using only core electrons [7]: 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

3. Any electron with a lower n value 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 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

b. Using Slater’s rules [6, 9]: This method adjusts for shielding but still assumes all orbitals penetrate

in the same way. This gives us a slightly lower Zeff value, but still does not differentiate between

s and p orbitals. To find S:

1. Write the electron configuration of the atom:

B: 1s2 2s2 2p1

2. make the following groups: (1s) (2s2p) (3s3p) (3d) (4s4p) (4d) (4f), etc.:

B: (1s2) (2s2 2p1)

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

If we choose one of the 2s electrons n = 2

4. Any electrons in groups to the right of the electron of interest contribute nothing to S:

There are no groups to the right of the group with the 2s electron.

5. Any electrons in the same group contribute 0.35 to S:

There is one more s electron and one p electron in the group

S = (0.35)(2) = 0.70

6. Any electrons with a size number of n – 1 contribute 0.85 to S:

There are 2 total electrons with n = 1

S = (0.85)(2) = 1.70
 7. Any electrons with an n - 2 value or lower contribute 1 unit to S:

There are no electrons with an n – 2 value.

Using this method, the shielding constant for a 2s electron would be S = 0.70 + 1.70 = 2.40, and

the effective nuclear charge would then be:

Zeff = 5 – 2.4 = 2.6

c. Using Clementi’s shielding factors [2]: This method accurately gives different effective nuclear

charges for 2s and 2p electrons but unlike the other methods requires the use of the table of

shielding factors referenced in [2]. In these formulas N2s and N2p are the number of electrons in

the 2s and 2p orbitals. To calculate S:

B: 1s22s22p1

For 2s electrons:

S = 1.7208 + 0.3601(N2s – 1 + N2p)

1.7208 + 0.3601(2 – 1 + 1)

S = 2.44

Zeff = 5 – 2.44 = 2.56

For 2p electrons:

S = 2.5787 + 0.3326(N2p – 1)

2.5787 + 0.3326(1 – 1)

S = 2.5787

Zeff = 5 – 2.5787 = 2.42

 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]

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]

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 [4, 10] to the strength of materials [8], to their electrical conductivity [5]
 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.