Electron configuration

In atomic physics and quantum

chemistry, the electron
configuration is the distribution
of electrons of
an atom ormolecule (or other
physical structure)
in atomic or molecular orbitals.
[1] For example, the electron
configuration of theneon atom is
1s2 2s2 2p6.
Electronic configurations describe electrons as each moving independently in an
orbital, in an average field created by all other orbitals. Mathematically, configurations
are described by Slater determinants or configuration state functions.
According to the laws of quantum mechanics, for systems with only one electron, an
energy is associated with each electron configuration and, upon certain conditions,
electrons are able to move from one configuration to another by the emission or
absorption of a quantum of energy, in the form of a photon.
Knowledge of the electron configuration
of different atoms is useful in understanding
the structure of the periodic table of elements.
The concept is also useful for describing the
chemical bonds that hold atoms together. In
n=
bulk materials, this same idea helps explain
1
the peculiar properties
of lasers and semiconductors.

Shells and subshells

Electron configuration was first
conceived of under the Bohr model of the
atom, and it is still common to speak of shells
and subshells despite the advances in
n=
understanding of the quantum2
mechanical nature of electrons.

s ( =0)

p ( =1)

m=0

m=0

pz

m=1
px

py

An electron shell is the set of allowed states that share the same principal quantum
number, n (the number before the letter in the orbital label), that electrons may occupy.
An atom's nth electron shell can accommodate 2n2 electrons, e.g. the first shell can
accommodate 2 electrons, the second shell 8 electrons, and the third shell 18 electrons.
The factor of two arises because the allowed states are doubled due to electron spin
each atomic orbital admits up to two otherwise identical electrons with opposite spin, one
with a spin +1/2 (usually denoted by an up-arrow) and one with a spin 1/2 (with a
down-arrow).
A subshell is the set of states defined by a common azimuthal quantum number, ,
within a shell. The values = 0, 1, 2, 3 correspond to the s, p, d, and f labels, respectively.
The maximum number of electrons that can be placed in a subshell is given by 2(2 + 1).
This gives two electrons in an s subshell, six electrons in a p subshell, ten electrons in a
d subshell and fourteen electrons in an f subshell.
The numbers of electrons that can occupy each shell and each subshell arise from
the equations of quantum mechanics, in particular the Pauli exclusion principle, which
states that no two electrons in the same atom can have the same values of the
four quantum numbers.

Notation
Physicists and chemists use a standard notation to indicate the electron
configurations of atoms and molecules. For atoms, the notation consists of a sequence of
atomic orbital labels (e.g. for phosphorus the sequence 1s, 2s, 2p, 3s, 3p) with the number
of electrons assigned to each orbital (or set of orbitals sharing the same label) placed as a
superscript. For example, hydrogen has one electron in the s-orbital of the first shell, so
its configuration is written 1s1. Lithium has two electrons in the 1s-subshell and one in
the (higher-energy) 2s-subshell, so its configuration is written 1s2 2s1 (pronounced "one-stwo, two-s-one"). Phosphorus (atomic number 15) is as follows: 1s2 2s2 2p6 3s2 3p3.
For atoms with many electrons, this notation can become lengthy and so an
abbreviated notation is used, since all but the last few subshells are identical to those of
one or another of the noble gases. Phosphorus, for instance, differs
from neon (1s2 2s2 2p6) only by the presence of a third shell. Thus, the electron
configuration of neon is pulled out, and phosphorus is written as follows: [Ne] 3s2 3p3.
This convention is useful as it is the electrons in the outermost shell that most determine
the chemistry of the element.
For a given configuration, the order of writing the orbitals is not completely fixed
since only the orbital occupancies have physical significance. For example, the electron
configuration of the titanium ground state can be written as either [Ar] 4s2 3d2 or
[Ar] 3d2 4s2. The first notation follows the order based on the Madelung rule for the
configurations of neutral atoms; 4s is filled before 3d in the sequence Ar, K, Ca, Sc, Ti.
The second notation groups all orbitals with the same value of n together, corresponding
to the "spectroscopic" order of orbital energies that is the reverse of the order in which
electrons are removed from a given atom to form positive ions; 3d is filled before 4s in
the sequence Ti4+, Ti3+, Ti2+, Ti+, Ti.

The superscript 1 for a singly occupied orbital is not compulsory. It is quite common
to see the letters of the orbital labels (s, p, d, f) written in an italic or slanting typeface,
although the International Union of Pure and Applied Chemistry (IUPAC) recommends a
normal typeface (as used here). The choice of letters originates from a now-obsolete
system of categorizing spectral lines as "sharp", "principal", "diffuse" and "fundamental"
(or "fine"), based on their observed fine structure: their modern usage indicates orbitals
with an azimuthal quantum number, l, of 0, 1, 2 or 3 respectively. After "f", the sequence
continues alphabetically "g", "h", "i"... (l = 4, 5, 6...), skipping "j", although orbitals of
these types are rarely required.[4][5]
The electron configurations of molecules are written in a similar way, except
that molecular orbital labels are used instead of atomic orbital labels (see below).

Energy ground state and excited states

The energy associated to an electron is that of its orbital. The energy of a
configuration is often approximated as the sum of the energy of each electron, neglecting
the electron-electron interactions. The configuration that corresponds to the lowest
electronic energy is called the ground state. Any other configuration is an excited state.
As an example, the ground state configuration of the sodium atom is 1s22s22p63s, as
deduced from the Aufbau principle (see below). The first excited state is obtained by
promoting a 3s electron to the 3p orbital, to obtain the 1s22s22p63p configuration,
abbreviated as the 3p level. Atoms can move from one configuration to another by
absorbing or emitting energy. In a sodium-vapor lamp for example, sodium atoms are
excited to the 3p level by an electrical discharge, and return to the ground state by
emitting yellow light of wavelength 589 nm.
Usually, the excitation of valence electrons (such as 3s for sodium) involves energies
corresponding to photons of visible or ultraviolet light. The excitation of core electrons is
possible, but requires much higher energies, generally corresponding to x-ray photons.
This would be the case for example to excite a 2p electron to the 3s level and form the
excited 1s22s22p53s2 configuration.
The remainder of this article deals only with the ground-state configuration, often
referred to as "the" configuration of an atom or molecule.

History
Niels Bohr (1923) was the first to propose that the periodicity in the properties of the
elements might be explained by the electronic structure of the atom.[6] His proposals
were based on the then current Bohr model of the atom, in which the electron shells were
orbits at a fixed distance from the nucleus. Bohr's original configurations would seem
strange to a present-day chemist: sulfur was given as 2.4.4.6 instead of
1s2 2s2 2p6 3s2 3p4 (2.8.6).
The following year, E.C.Stoner incorporated Sommerfeld's third quantum number into
the description of electron shells, and correctly predicted the shell structure of sulfur to be
2.8.6.[7] However neither Bohr's system nor Stoner's could correctly describe the changes
in atomic spectra in a magnetic field (the Zeeman effect).

Bohr was well aware of this shortcoming (and others), and had written to his
friend Wolfgang Pauli to ask for his help in saving quantum theory (the system now
known as "old quantum theory"). Pauli realized that the Zeeman effect must be due only
to the outermost electrons of the atom, and was able to reproduce Stoner's shell structure,
but with the correct structure of subshells, by his inclusion of a fourth quantum number
and his exclusion principle (1925):[8]
It should be forbidden for more than one electron with the same value of the main
quantum number n to have the same value for the other three quantum
numbers k[l], j [ml] and m [ms].
The Schrdinger equation, published in 1926, gave three of the four quantum
numbers as a direct consequence of its solution for the hydrogen atom:[2] this solution
yields the atomic orbitals that are shown today in textbooks of chemistry (and above).
The examination of atomic spectra allowed the electron configurations of atoms to be
determined experimentally, and led to an empirical rule (known as Madelung's rule
(1936),[9] see below) for the order in which atomic orbitals are filled with electrons.

Atoms: Aufbau principle and Madelung rule

The Aufbau principle was an important part of Bohr's original concept of electron
configuration. It may be stated as:
a maximum of two electrons are put into orbitals in the order of increasing orbital
energy: the lowest-energy orbitals are filled before electrons are placed in higherenergy orbitals.
The principle works very well (for the ground states of the atoms) for the first
18 elements, then decreasingly well for the following 100 elements. The modern form of
the Aufbau principle describes an order of orbital energies given by Madelung's rule (or
Klechkowski's rule). This rule was first stated by Charles Janet in 1929, rediscovered
by Erwin Madelung in 1936,[9]and later given a theoretical justification by V.M.
Klechkowski
1. Orbitals are filled in the order of increasing n+l;
2. Where two orbitals have the same value of n+l, they are filled in order of
increasing n.
This gives the following order for filling the orbitals:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p, (8s, 5g, 6f, 7d,
8p, and 9s)
In this list the orbitals in parentheses are not occupied in the ground state of the heaviest
atom now known (Uuo, Z = 118).
The Aufbau principle can be applied, in a modified form, to the protons and neutrons in
the atomic nucleus, as in the shell model of nuclear physics and nuclear chemistry.

Periodic table

The form of the periodic table is closely related to the electron configuration of the
atoms of the elements. For example, all the elements of group 2 have an electron
configuration of [E] ns2 (where [E] is an inert gasconfiguration), and have notable
similarities in their chemical properties. In general, the periodicity of the periodic table in
terms of periodic table blocks is clearly due to the number of electrons (2, 6, 10, 14...)
needed to fill s, p, d, and f subshells.
The outermost electron shell is often referred to as the "valence shell" and (to a first
approximation) determines the chemical properties. It should be remembered that the
similarities in the chemical properties were remarked on more than a century before the
idea of electron configuration.[12] It is not clear how far Madelung's rule explains (rather
than simply describes) the periodic table,[13] although some properties (such as the
common +2 oxidation state in the first row of the transition metals) would obviously be
different with a different order of orbital filling.

Shortcomings of the Aufbau principle

The Aufbau principle rests on a fundamental postulate that the order of orbital
energies is fixed, both for a given element and between different elements; in both cases
this is only approximately true. It considers atomic orbitals as "boxes" of fixed energy
into which can be placed two electrons and no more. However, the energy of an electron
"in" an atomic orbital depends on the energies of all the other electrons of the atom (or
ion, or molecule, etc.). There are no "one-electron solutions" for systems of more than
one electron, only a set of many-electron solutions that cannot be calculated
exactly[14] (although there are mathematical approximations available, such as
the HartreeFock method).
The fact that the Aufbau principle is based on an approximation can be seen from the
fact that there is an almost-fixed filling order at all, that, within a given shell, the s-orbital
is always filled before the p-orbitals. In a hydrogen-like atom, which only has one
electron, the s-orbital and the p-orbitals of the same shell have exactly the same energy, to
a very good approximation in the absence of external electromagnetic fields. (However,
in a real hydrogen atom, the energy levels are slightly split by the magnetic field of the
nucleus, and by the quantum electrodynamic effects of the Lamb shift.)

Ionization of the transition metals

The nave application of the Aufbau principle leads to a well-known paradox (or
apparent paradox) in the basic chemistry of the transition
metals. Potassium and calcium appear in the periodic table before the transition metals,
and have electron configurations [Ar] 4s1 and [Ar] 4s2 respectively, i.e. the 4s-orbital is
filled before the 3d-orbital. This is in line with Madelung's rule, as the 4s-orbital has n+l
= 4 (n = 4, l = 0) while the 3d-orbital has n+l = 5 (n = 3, l = 2). After calcium, most
neutral atoms in the first series of transition metals (Sc-Zn) have configurations with two
4s electrons, but there are two exceptions. Chromium and copper have electron
configurations [Ar] 3d5 4s1 and [Ar] 3d10 4s1respectively, i.e. one electron has passed from
the 4s-orbital to a 3d-orbital to generate a half-filled or filled subshell. In this case, the
usual explanation is that "half-filled or completely filled subshells are particularly stable
arrangements of electrons".

The apparent paradox arises when electrons are removed from the transition metal
atoms to form ions. The first electrons to be ionized come not from the 3d-orbital, as one
would expect if it were "higher in energy", but from the 4s-orbital. This interchange of
electrons between 4s and 3d is found for all atoms of the first series of transition metals.
[15]The configurations of the neutral atoms (K, Ca, Sc, Ti, V, Cr, ...) usually follow the
order 1s, 2s, 2p, 3s, 3p, 4s, 3d, ...; however the successive stages of ionization of a given
atom (such as Fe4+, Fe3+, Fe2+, Fe+, Fe) usually follow the order 1s, 2s, 2p, 3s, 3p, 3d,
4s, ...
This phenomenon is only paradoxical if it is assumed that the energy order of atomic
orbitals is fixed and unaffected by the nuclear charge or by the presence of electrons in
other orbitals. If that were the case, the 3d-orbital would have the same energy as the 3porbital, as it does in hydrogen, yet it clearly doesn't. There is no special reason why the
Fe2+ ion should have the same electron configuration as the chromium atom, given
that iron has two more protons in its nucleus than chromium, and that the chemistry of the
two species is very different. Melrose and Eric Scerri have analyzed the changes of
orbital energy with orbital occupations in terms of the two-electron repulsion integrals of
theHartree-Fock method of atomic structure calculation.[16]
Similar ion-like 3dx4s0 configurations occur in transition metal complexes as
described by the simple crystal field theory, even if the metal has oxidation state 0. For
example,chromium hexacarbonyl can be described as a chromium atom (not ion)
surrounded by six carbon monoxide ligands. The electron configuration of the central
chromium atom is described as 3d6 with the six electrons filling the three lower-energy d
orbitals between the ligands. The other two d orbitals are at higher energy due to the
crystal field of the ligands. This picture is consistent with the experimental fact that the
complex is diamagnetic, meaning that it has no unpaired electrons. However, in a more
accurate description using molecular orbital theory, the d-like orbitals occupied by the six
electrons are no longer identical with the d orbitals of the free atom.

Other exceptions to Madelung's rule

There are several more exceptions to Madelung's rule among the heavier elements,
and it is more and more difficult to resort to simple explanations, such as the stability of
half-filled subshells. It is possible to predict most of the exceptions by HartreeFock
calculations,[17] which are an approximate method for taking account of the effect of the
other electrons on orbital energies. For the heavier elements, it is also necessary to take
account of the effects of Special Relativity on the energies of the atomic orbitals, as the
inner-shell electrons are moving at speeds approaching the speed of light. In general,
these relativistic effects[18] tend to decrease the energy of the s-orbitals in relation to the
other atomic orbitals.[19] The table below shows the ground state configuration in terms
of orbital occupancy, but it does not show the ground state in terms of the sequence of
orbital energies as determined spectroscopically. For example, in the transition metals, the
4s orbital is of a higher energy than the 3d orbitals; and in the lanthanides, the 6s is higher
than the 4f and 5d. The ground states can be seen in the Electron configurations of the
elements (data page).
Electron shells filled in violation of Madelung's rule[20] (red)
Period 4
Period 5
Period 6
Period 7

Electr
on
Elem
Z Config
ent
uratio
n

Electr
on
Elem
Z Config
ent
uratio
n

Electr
on
Eleme
Z Config
nt
uratio
n

Electr
on
Eleme
Z Config
nt
uratio
n

Lantha 5 [Xe]
num
7 6s2 5d1

Actini
um

8 [Rn]
9 7s2 6d1

Cerium

[Xe]
5
6s2 4f1
8
5d1

Thoriu 9 [Rn]
m
0 7s2 6d2

Praseo
dymiu
m

5 [Xe]
9 6s2 4f3

[Rn]
Protact 9
7s2 5f2
inium 1
6d1

Neody
mium

6 [Xe]
0 6s2 4f4

[Rn]
Uraniu 9
7s2 5f3
m
2
6d1
[Rn]
9
7s2 5f4
3
6d1

Promet 6 [Xe]
hium
1 6s2 4f5

Neptu
nium

Samari 6 [Xe]
um
2 6s2 4f6

Plutoni 9 [Rn]
um
4 7s2 5f6

Europi
um

6 [Xe]
3 6s2 4f7

Ameri
cium

9 [Rn]
5 7s2 5f7

Gadoli
nium

[Xe]
6
6s2 4f7
4
5d1

Curiu
m

[Rn]
9
7s2 5f7
6
6d1

Terbiu
m

6 [Xe]
5 6s2 4f9

Berkel 9 [Rn]
ium
7 7s2 5f9

Yttriu 3 [Kr]
m
9 5s2 4d1

[Xe]
Lutetiu 7
6s2 4f14
m
1
5d1

Lawre
ncium

Titani 2 [Ar]
um
2 4s2 3d2

Zirco
nium

4 [Kr]
0 5s2 4d2

[Xe]
Hafniu 7
6s2 4f14
m
2
5d2

Ruther 1 [Rn]
fordiu 0 7s2 5f14
m
4 6d2

Vana
dium

Niobi
um

4 [Kr] 5s
1 1 4d4

[Xe]
Tantalu 7
6s2 4f14
m
3
5d3

Scan
dium

2 [Ar]
1 4s2 3d1

2 [Ar]
3 4s2 3d3

Chro 2 [Ar] 4s
mium 4 1 3d5

Moly
4 [Kr] 5s
bdenu
2 1 4d5
m

Tungst
en

[Xe]
7
6s2 4f14
4
5d4

1 [Rn]
0 7s2 5f14
3 7p1

Mang 2 [Ar]
anese 5 4s2 3d5

Techn 4 [Kr]
etium 3 5s2 4d5

[Xe]
Rheniu 7
6s2 4f14
m
5
5d5

2 [Ar]
6 4s2 3d6

Ruthe 4 [Kr] 5s
nium 4 1 4d7

Osmiu
m

Cobal 2 [Ar]
t
7 4s2 3d7

Rhodi 4 [Kr] 5s
um
5 1 4d8

[Xe]
7
Iridium
6s2 4f14
7
5d7

[Ar]
4s2 3d8
or
Nicke 2
[Ar] 4s
l
8 1 9
3d (di
sputed)
[21]

Pallad 4 [Kr] 4d
ium
6 10

Platinu 7
m
8

[Xe] 6s
1
4f14 5
9
d

Copp 2 [Ar] 4s
er
9 1 3d10

4 [Kr] 5s
Silver
7 1 4d10

Gold

7
9

[Xe] 6s
1
4f14 5
d10

[Ar]
3
4s2 3d1
0 0

[Kr]
Cadm 4
5s2 4d1
ium
8 0

[Xe]
Mercur 8
6s2 4f14
y
0
5d10

Iron

Zinc

[Xe]
7
6s2 4f14
6
5d6

The electron-shell configuration of elements beyond rutherfordium has not yet been
empirically verified, but they are expected to follow Madelung's rule without exceptions
untilelement 120.[22]

Electron configuration in molecules

In molecules, the situation becomes more complex, as each molecule has a different
orbital structure. The molecular orbitals are labelled according to their symmetry,
[23] rather than the atomic orbital labels used for atoms and monatomic ions: hence, the
electron configuration of the dioxygen molecule, O2, is written
1g2 1u2 2g2 2u2 3g2 1u4 1g2,[24][25] or equivalently 1g2 1u2 2g2 2u2 1u4 3g2 1g2.
[1] The term 1g2 represents the two electrons in the two degenerate *-orbitals
(antibonding). From Hund's rules, these electrons have parallel spins in the ground state,
and so dioxygen has a net magnetic moment (it is paramagnetic). The explanation of the
paramagnetism of dioxygen was a major success for molecular orbital theory.
The electronic configuration of polyatomic molecules can change without absorption
or emission of a photon through vibronic couplings.

Electron configuration in solids

In a solid, the electron states become very numerous. They cease to be discrete, and
effectively blend into continuous ranges of possible states (an electron band). The notion
of electron configuration ceases to be relevant, and yields to band theory.

Applications
The most widespread application of electron configurations is in the rationalization
of chemical properties, in both inorganic and organic chemistry. In effect, electron
configurations, along with some simplified form of molecular orbital theory, have
become the modern equivalent of the valence concept, describing the number and type of
chemical bonds that an atom can be expected to form.
This approach is taken further in computational chemistry, which typically attempts
to make quantitative estimates of chemical properties. For many years, most such
calculations relied upon the "linear combination of atomic orbitals" (LCAO)
approximation, using an ever larger and more complex basis set of atomic orbitals as the
starting point. The last step in such a calculation is the assignment of electrons among the
molecular orbitals according to the Aufbau principle. Not all methods in calculational
chemistry rely on electron configuration: density functional theory (DFT) is an important
example of a method that discards the model.
For atoms or molecules with more than one electron, the motion of electrons
are correlated and such a picture is no longer exact. A very large number of electronic
configurations are needed to exactly describe any multi-electron system, and no energy
can be associated with one single configuration. However, the electronic wave function is
usually dominated by a very small number of configurations and therefore the notion of
electronic configuration remains essential for multi-electron systems.
A fundamental application of electron configurations is in the interpretation
of atomic spectra. In this case, it is necessary to supplement the electron configuration
with one or more term symbols, which describe the different energy levels available to an
atom. Term symbols can be calculated for any electron configuration, not just the groundstate configuration listed in tables, although not all the energy levels are observed in
practice. It is through the analysis of atomic spectra that the ground-state electron
configurations of the elements were experimentally determined.