Found Chem (2016) 18:57–65

DOI 10.1007/s10698-016-9249-0

The 4s and 3d subshells: Which one fills first

in progressing through the periodic table and which one
fills first in any particular atom?

Sadegh Salehzadeh1 • Farahnaz Maleki1

Published online: 1 February 2016

 Springer Science+Business Media Dordrecht 2016

Abstract In this paper, first we discuss an old problem in teaching electron configura-
tion of transition metals and the order in which the orbitals are filled. Then we propose two
simple computational experiments, in order to show that in the case of first row transition
metals and the main group elements after them, the electrons occupy the 3d subshell before
the 4s. It is shown that if we begin with the bare nucleus of above elements in the vacuum
and then continue with adding the electrons the 19th electron firstly occupies the 3d sub-
shell and not the 4s. Indeed, the 4s subshell in the third row of periodic table only fills first
in the case of K and Ca atoms. However, the 3d subshell in transition metals and the main
group elements after them is more stable than 4s and so fills first. Thus there is no scientific
reason to write the electron configuration of transition elements as [Ar] 4s 3d and the
correct form is [Ar] 3d 4s.

Electronic supplementary material The online version of this article (doi:10.1007/s10698-016-9249-0)

contains supplementary material, which is available to authorized users.

& Sadegh Salehzadeh

[email protected]
1
Faculty of Chemistry, Bu-Ali Sina University, Hamadan, Iran

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58 S. Salehzadeh, F. Maleki

Graphical Abstract

Keywords Electron configuration
3d and 4s orbitals
Transition metals
Periodic

table
Theoretical study

Introduction

The electron configuration of an atom is the representation of the distribution of electrons

among the orbital shells and subshells. Commonly, the electron configuration is used to
describe the orbitals of an atom in its ground state, but it can also be used to represent an
atom that is ionized into a cation or anion. Many of the physical and/or chemical properties
of elements are related to their electron configuration. On the other hand, the valence
electrons, electrons in the outermost shell, are the determining factor for the unique
chemistry of each element. Several papers have been published about the electron con-
figuration of atoms (Deeley 1893; Eichinger 1957, 1959; Dickens and Linnett 1957;
Sanderson 1960; Krupsaw and Ng 1972; Carpenter 1983; Grenda 1988; Darsey 1988;
Scerri 1989, 2007, 2012, 2013a, b, 2015; Rleck 1990; Vanquickenborne et al. 1994; Lza
and Gil 1995; Viossat 2000; Toomey et al. 2001; Barke and Wirbs 2002; Nelson 2002).
Unfortunately, the electron configuration of transition metals appear in two different types
in the chemistry text books. In one type the (n - 1)d subshell is placed first after the
symbol of its previous noble gas (Type I), but in other type the ns orbital is the first (type
II). For example, among the textbooks in our personal library, the electron configuration of
first row transition metals, in some cases (Huheey et al. 1993; Mortimer 1986; Ebbing
2009; House and House 2010; Atkins et al. 2010; Whitten et al. 2013; Scerri 2013a, b) is
shown as type I and in others (Silberberg 2007; Housecroft and Sharpe 2008, Housecroft
and Constable 2010; Canham 2010; Beier 2010; Petrucci et al. 2011; Chang and Overby
2011; Zumdahl 2012; McMurry et al. 2012; Miessler et al. 2014) as Type II.

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The 4s and 3d subshells: Which ones fill first in… 59

Type I [Ar] 3d 4s
Type II [Ar] 4s 3d
Indeed, the authors who write the electron configuration of transition metals as type I,
explain that the orbitals are listed according to their principal quantum number and/or their
relative energy. On the other hand, those authors who write the electron configuration of
transition metals as type II, usually explain that the orbitals are listed in the order in which
they fill. Of course, when we write the electron configuration of transition metal as type II
and we say that the orbitals are listed in the order in which they fill, students have the right
to conclude that the electrons occupy the 4s orbital before the 3d orbitals. The above
incorrect conclusion arises also from the fact that in the K and Ca atoms the 4s orbital is
filled before the 3d orbitals. Thus, students conclude that in the next elements of fourth row
of the periodic table the electrons occupy the 3d subshell after the 4s and the outermost
electrons are those in the 3d subshell. Thus, due to this incorrect conclusion students can
hardly understand that in the ionization process the transition elements loose the 4s elec-
trons first. In order to solve this problem, we must make clear the difference between the
following two completely different statements for electron configuration of single atom of
elements in vacuum:
(a) In the periodic table of elements when we follow the electron configuration of
elements one after the other we see that the orbitals fill as following order: 1s, 2s, 2p,
3s, 3p, 4s, 3d (see Fig. 1a). Thus the 4s subshell in the periodic table is filled before
the 3d.
(b) In each element when we follow the occupation of electrons and the order in which
the orbitals are filled, we see that the orbitals fill as following order: 1s, 2s, 2p, 3s,
3p, 4s, 3d. Thus the 4s subshell in each element is filled before the 3d.
Indeed, everybody knows that the first statement is really correct because when we
review the elements of the periodic table we see that in 19th and 20th elements of the
periodic table the electron has occupied the 4s subshell before the 3d. However, the second
statement expresses that the 19th and 20th electrons in all elements occupy the 4s subshell
before the 3d and this is not correct (see Fig. 1b). Fortunately, based on several valuable

Fig. 1 Reviewing the elements in ‘‘periodic table’’ (a) and reviewing the occupation of electrons in ‘‘each
element’’ (b) to check the order in which the orbitals are filled

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60 S. Salehzadeh, F. Maleki

scientific papers which are published by Schwarz and Rich (2010), Wang et al. (2006),
Wang and Schwarz (2009) and educational papers published by Scerri (2013a, b, 2015) in
recent years we know that in the fourth row of the periodic table the electron occupies the
4s subshell before the 3d only in the case of K and Ca atoms. Thus statement (b) is correct
only for some special elements like K and Ca. On the other hand, as we mentioned above,
all transition metals in the ionization/oxidation process lose the 4s electrons first, indicating
that these are the least stable electrons. Indeed, in the case of transition elements the
4s orbital neither fills first nor is more stable than 3d. Therefore, there is no logical reason
to write the electron configuration of transition metals and main group elements after them
as type II. Unfortunately, we still see in some well-known chemistry text books (Petrucci
et al. 2011; Chang and Overby 2011; Zumdahl 2012; McMurry et al. 2012; Miessler et al.
2014), which were published after Schwarz’s papers, that the electron configuration of
transition metals appear as type II. Thus it seems that, it is still necessary to discuss the
electron configurations of transition metals and the order in which orbitals fill. In this paper
we propose two simple computational experiments to make clear how the orbitals fill in
vacuum, one after the other and in which cases the 4s orbital fills before the 3d.
It should be noted that the electron configuration of some elements in the pure or
composite chemical substances is different with that in the vacuum (Wang and Schwarz
2009) and is not the subject of present study.

Computational details

In the first experiment we assumed that for any atom initially there is only a bare nucleus
and we put the electrons, one after the other, around this nucleus to build the whole atom.
The electrons will occupy the orbitals one after another and we can readily follow this
process. For the above study we chose the K, Ca, Sc, Mn, Zn, and Ge atoms. Also for the
second experiment we chose the S3-, Cl2- and Ar- anions, K atom and Ca?, Sc2?, Ti3?,
V4?, Cr5?, Mn6?, Fe7?, Co8?, Ni9?, Cu10?, Zn11?, Ga12? and Ge13? cations, all of which
have 19 electrons. We check whether a 4s or 3d orbital receives the 19th electron in the
above species. All calculations for the first experiment were performed at M06/def2-
QZVPP and M06/6-311??G** levels of theory and for the second experiment at M06/6-
311??G** level of theory using the Gaussian 09 (Frisch et al. 2009) set of programs.

Results and discussion

The results of the first and second computational experiments proposed here are shown in
Table 1 and Fig. 2, respectively. First let us to discuss the first experiment and corre-
sponding data shown in Table 1. As can be seen, the calculations clearly confirm that when
we want to build the K, Ca, Sc, Mn, Zn and Ge atoms by addition of electrons around their
nucleus, then in all cases the first 18 electrons occupy the 1s, 2s, 2p, 3s and 3p subshells
one after the other. However, the difference begins when the 19th electron is added around
the nucleus. As can be seen, in the case of K and Ca, the 19th electron occupies the
4s orbital but in Sc, Mn, Zn and Ge it occupies one of 3d orbitals. The 20th electron in Ca
and Sc atoms fills the 4s orbital but in Mn, Zn and Ge atoms it occupies the 3d subshell. It
is interesting that in Mn only five electrons occupy the 3d subshell and the 24th and the
25th electrons go into the 4s orbital. In the case of the Zn atom from the 19th electron until

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The 4s and 3d subshells: Which ones fill first in… 61

Table 1 The electron configuration of ions/atoms produced form the addition of n electrons around the
nucleus of K, Ca, Sc, Mn, Zn and Ge atoms
N 19K 20Ca 21Sc 25Mn 30Zn 32Ge

19 [Ar]4s1 [Ar]4s1 [Ar]3d1 [Ar]3d1 [Ar]3d1 [Ar]3d1

2 1 1 2 2
20 [Ar]4s [Ar]3d 4s [Ar]3d [Ar]3d [Ar]3d2
1 2 3 3
21 [Ar]3d 4s [Ar]3d [Ar]3d [Ar]3d3
4 4
22 [Ar]3d [Ar]3d [Ar]3d4
5 5
23 [Ar]3d [Ar]3d [Ar]3d5
5 1 6
24 [Ar]3d 4s [Ar]3d [Ar]3d6
5 2 7
25 [Ar]3d 4s [Ar]3d [Ar]3d7
8
26 [Ar]3d [Ar]3d8
9
27 [Ar]3d [Ar]3d9
10
28 [Ar]3d [Ar]3d10
10 1
29 [Ar]3d 4s [Ar]3d104s1
10 2
30 [Ar]3d 4s [Ar]3d104s2
31 [Ar]3d104s24p1
32 [Ar]3d104s24p2
In all cases for 1st to 18th electron occupation goes in the order 1s2, 2s2, 2p6, 3s2, 3p6
The energy of all atomic orbitals are given in supporting information

70

4s
-30
3d

-130

-230

-330

-430

-530

-630

Fig. 2 The relative energies (eV) of 3d and 4s orbitals in studied atom/ions, which shows whether the 19th
electron has occupied the 3d or 4s subshell. Note that only the S3-, Cl2-, Ar-, K and Ca? has 4s1 3d0
electron configuration

28th electrons go into the 3d subshell and 29th and 30th electrons occupy the 4s subshell.
Thus in the cases of Mn and Zn the last two electrons occupy the 4s subshell. In the case of
the Ge atom, similar to the Zn atom, the 19th electron until the 28th electron go into the
3d subshell, 29th and 30th electrons occupy the 4s subshell and the last two electrons go
into the 4p subshell. Thus the data indicate that among the above six studied atoms the
electrons occupy the 4s subshell first only in the case of potassium and calcium. Now let us
review the results of the second experiment. First it should be noted that in this experiment

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62 S. Salehzadeh, F. Maleki

we have chosen a number of anions and cations that do not exist and/or are not
stable species in reality. However, we want to see the location of 19th electron when we
add/remove one, two or several electrons to/from one stable and known atom that has 19
electrons. As can be seen in Fig. 2, in S3-, Cl2-, Ar- anions, K atom and Ca? cation the
19th electron occupies the 4s subshell and the electron configuration is 4s13d0. However, in
all remaining Mn? ions of the fourth row of the periodic table having 19 electrons, the last
electron occupies the 3d subshell and electron configuration is 3d14s0. Indeed, before the
fourth row and also in the left side of this row, for every atom/ion having 19 electrons the
4s orbital is more stable than 3d orbitals. However, beginning from the Sc2? ion the
3d subshell becomes more stable than 4s one and as we go to the right side of the row the
energy difference between them significantly increases. We note that in Kr17? the
3d subshell is about 261.83 eV more stable than 4s. Thus when we add the 19th electron to
such ions/atoms the 4s subshell has absolutely no chance of receiving the electron before
the 3d subshell. Indeed, when we add an electron to the ions/atoms having the electron
configuration of Ar atom but different atomic numbers (Z), then the electron occupies the
4s for Z \ 21 and occupies the 3d subshell in the cases of atoms/ions with Z C 21. Thus
the second experiment also shows that in the process of building the atoms of elements in
fourth row of the periodic table by addition of electrons around their nucleus, the 19th
electron occupies the 3d subshell in all cases except the K and Ca atoms. Now the question
is that if the 3d is more stable than 4s why don’t all of valence electrons occupy the
3d subshell and usually two or one electrons occupy the 4s subshell? A complete answer to
above question can be found in Schwarz and Wang papers (2010) and Wang et al. (2006) .
However, herein we give a simplified format of above answer that can be understood by all
readers and even students. Indeed, usually the ground configuration can be predicted from
the order of orbital energies but only when the difference between the electron repulsion
energies of different configurations is not larger than the energy difference between the
orbital energies. Whenever the electron repulsion energies decrease significantly, while the
electron goes to a less stable orbital and its energy increases slightly, the energy of the
whole atom decreases. Thus a 3dn-m 4sm electron configuration can be more stable than a
3dn configuration while the 4s orbital is less stable than 3d. We note that in Sc the 20th
electron goes into 4s, in Mn the 24th electron goes to 4s and in Zn the 29th goes into
4s. Indeed the electron cannot go to 4s and goes into 3d until the energy difference between
the 3d and 4s subshells decreases significantly (see Fig. 3). Crystal field theory explains
similarly the high spin electron configuration in octahedral complexes where the energy
difference between the t2g and e.g. orbitals is small. The fourth electron does not remain in
more stable t2g orbital and goes to the less stable e.g. orbital because the electron repulsion
decreases significantly and the electronic energy will be slightly more stable if this occurs.
Recently, further explanation has also been given by Scerri (2013a, b) in his recent pub-
lished paper that we add it here with his permission:
It is natural to question why one or two electrons are usually pushed into a higher
energy orbital. The answer is because 3d orbitals are more compact than 4s, and as a
result any electrons entering 3d orbitals will experience greater mutual repulsion.
The slightly unsettling feature is that although the relevant s orbital can relieve such
additional electron–electron repulsion, different atoms do not always make full use
of this form of sheltering because the situation is more complicated than just
described. One thing to consider is that nuclear charge increases as we move through
the atoms, and there is a complicated set of interactions between the electrons and the
nucleus as well as between the electrons themselves. This is what ultimately

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The 4s and 3d subshells: Which ones fill first in… 63

3d 3d
-10 -8
4s 4s
-30 -28

-50 -48

-68
-70
-88
-90
-108
-110
-128
-130
-148
-150 -168

-170 -188

20
3d 3d
4s 4s
-30
-30

-80 -80

-130
-130

-180

-180
-230

-230 -280

Fig. 3 Variation of energy level (eV) of 3d and 4s subshells when the last eleven electrons are added to the
nucleus of K, Sc, Mn and Zn

produces an electronic configuration and, contrary to what some educators may wish
for, there is no simple qualitative rule of thumb that can cope with this complicated
situation.

Conclusion

In this work we have discussed that while good and clear scientific papers have been
published in recent years about the electron configuration of transition metals, still the
electron configurations of these elements do not appear correctly in most chemistry text
books and therefore sometimes fail to teach students correctly. It is true that in the periodic
table of elements, when we review the electron configuration of elements row after row
and element after element we see that in the case of K and Ca atoms the 4s subshell is filled
before the 3d one. However, it is not correct to say that in the case of all elements, when we
follow the occupation of electrons we see that the 4s subshell is filled invariably before
3d. We have proposed two simple computational experiments for chemistry students in
order to make clear the fact that it is not correct to say the electrons always occupy the
4s subshell before the 3d one. Instead, it is now time to say ‘‘ when we add an electron to a

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64 S. Salehzadeh, F. Maleki

cation in the fourth row of the periodic table it always occupies the 3d subshell before the
4s except in K? and Ca2? ‘‘. Indeed, when we add an electron to an ion having 18 electrons
and with an atomic number less than 21, the electron occupies the 4s subshell. On the other
hand, when we add the electron to an ion with an atomic number equal or larger than 21,
then it occupies the 3d subshell. Thus we can assume that in all transition elements and
main group elements after them, the 3d subshell receives the electron before the 4s sub-
shell. Indeed, in all transition elements and main group elements after them the 3d is more
stable than 4s and also receives the electron before 4s. Thus we have no reason to write the
electron configuration of transition metals as {ns (n - 1)d}. The correct form which must
be regarded in all text books is {(n - 1)d ns}.

Acknowledgments The authors thank the support of the Bu-Ali Sina University. Special thanks to Prof.
Eric Scerri (at the University of California, Los Angeles, US) for his valuable comments and guidance).

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