Aufbau principle

Atomic build-up redirects here. For the spread of The order in which these orbitals are lled is given by the
nuclear weapons, see Nuclear proliferation.
n + rule, also known as the Madelung rule (after Erwin
Madelung), or the Janet rule or the Klechkowsky rule
The Aufbau principle states that, hypothetically, (after Charles Janet or Vsevolod Klechkovsky in some,
mostly French and Russian-speaking, countries), or the
electrons orbiting one or more atoms ll the lowest avail[2]
able energy levels before lling higher levels (e.g., 1s be- diagonal rule. Orbitals with a lower n + value are
n + values. In this confore 2s). In this way, the electrons of an atom, molecule, lled before those with higher
principal
quantum number and
text,
n
represents
the
or ion harmonize into the most stable electron congurathe
azimuthal
quantum
number;
the values = 0, 1, 2, 3
tion possible.
correspond to the s, p, d, and f labels, respectively.
Aufbau is a German noun that means construction or
building-up. The Aufbau principle is sometimes called The rule is based on the total number of nodes in the
atomic orbital, n + , which is related to the energy.[3]
the building-up principle or the Aufbau rule.
In the case of equal n + values, the orbital with a lower
The details of this building-up tendency are described n value is lled rst. The fact that most of the ground
mathematically by atomic orbital functions. Electron be- state congurations of neutral atoms ll orbitals followhavior is elaborated by other principles of atomic physics, ing this n + , n pattern was obtained experimentally,
such as Hunds rule and the Pauli exclusion principle. by reference to the spectroscopic characteristics of the
Hunds rule asserts that even if multiple orbitals of the elements.[4]
same energy are available, electrons ll unoccupied orbitals rst, before reusing orbitals occupied by other elec- The Madelung energy ordering rule applies only to neutral atoms in their ground state, and even in that case,
trons. But, according to the Pauli exclusion principle, in
order for electrons to occupy the same orbital, they must there are several elements for which it predicts congurations that dier from those determined experimentally.[5]
have dierent spins (1/2 and 1/2).
Copper, chromium, and palladium are common examA version of the Aufbau principle known as the nuclear ples of this property. According to the Madelung rule,
shell model is used to predict the conguration of protons the 4s orbital (n + = 4 + 0 = 4) is occupied before the
and neutrons in an atomic nucleus.[1]
3d orbital (n + = 3 + 2 = 5). The rule then predicts
the conguration of 29 Cu to be 1s2 2s2 2p6 3s2 3p6 4s2 3d9 ,
abbreviated [Ar]4s2 3d9 where [Ar] denotes the conguof Ar (the preceding noble gas). However the ex1 Madelung energy ordering rule ration
perimental electronic conguration of the copper atom is
[Ar]4s1 3d10 . By lling the 3d orbital, copper can be in
a lower energy state. Similarly, chromium takes the electronic conguration of [Ar]4s1 3d5 instead of [Ar]4s2 3d4 .
In this case, chromium has a half-full 3d shell. For palladium, the Madelung rule predicts [Kr]5s2 4d8 , but the
experimental conguration [Kr]4d10 diers in the placement of two electrons.

2 History
2.1 The Aufbau principle in the new quantum theory
The principle takes its name from the German, Aufbauprinzip, building-up principle, rather than being named
for a scientist. In fact, it was formulated by Niels Bohr
and Wolfgang Pauli in the early 1920s, and states that:

The states crossed by the same arrow have same n + value. The
arrow direction indicates the order of lling states.

5 FURTHER READING
explanation of the order of ionization of electrons in this
and other transition metals far more intelligible, given that
4s electrons are invariably preferentially ionized.[8]

3 See also
5s (=0)
5p (=1)

5d (=2)

5f (=3)

5g (=4)

In the old quantum theory, orbits with low angular momentum

(s- and p-orbitals) get closer to the nucleus.

This was an early application of quantum mechanics to

the properties of electrons, and explained chemical properties in physical terms. Each added electron is subject
to the electric eld created by the positive charge of the
atomic nucleus and the negative charge of other electrons
that are bound to the nucleus. Although in hydrogen there
is no energy dierence between orbitals with the same
principal quantum number n, this is not true for the outer
electrons of other atoms.
In the old quantum theory prior to quantum mechanics, electrons were supposed to occupy classical elliptical
orbits. The orbits with the highest angular momentum
are 'circular orbits outside the inner electrons, but orbits with low angular momentum (s- and p-orbitals) have
high orbital eccentricity, so that they get closer to the nucleus and feel on average a less strongly screened nuclear
charge.

2.2

The n + energy ordering rule

A periodic table in which each row corresponds to one

value of n + was suggested by Charles Janet in 1927.
In 1936, the German physicist Erwin Madelung proposed
his empirical rules for the order of lling atomic subshells, based on knowledge of atomic ground states determined by the analysis of atomic spectra, and most
English-language sources therefore refer to the Madelung
rule. Madelung may have been aware of this pattern as
early as 1926.[6] In 1962 the Russian agricultural chemist
V.M. Klechkowski proposed the rst theoretical explanation for the importance of the sum n + , based on
the statistical ThomasFermi model of the atom.[7] Many
French- and Russian-language sources therefore refer to
the Klechkowski rule. In recent years some authors have
challenged the validity of Madelungs rule in predicting
the order of lling of atomic orbitals. For example, it has
been claimed, not for the rst time, that in the case of the
scandium atom a 3d orbital is occupied before the occupation of the 4s orbital. In addition to there being ample
experimental evidence to support this view, it makes the

Electron conguration
Valence electrons
Wiswessers rule

4 References
[1] Cottingham, W. N.; Greenwood, D. A. (1986). Chapter
5: Ground state properties of nuclei: the shell model.
An introduction to nuclear physics. Cambridge University
Press. ISBN 0-521-31960-9.
[2] Electron Conguration. WyzAnt.
[3] Weinhold, Frank; Landis, Clark R. (2005). Valency and
bonding: A Natural Bond Orbital Donor-Acceptor Perspective. Cambridge: Cambridge University Press. pp. 715
716. ISBN 0-521-83128-8.
[4] Scerri, Eric R. (1998).
How Good is the
Quantum Mechanical Explanation of the Periodic System?" (PDF). J. Chem.
Ed.
75
(11):
138485.
Bibcode:1998JChEd..75.1384S.
doi:10.1021/ed075p1384 .
[5] Meek, Terry L.; Allen, Leland C. (2002). Conguration irregularities: deviations from the Madelung rule and
inversion of orbital energy levels. Chem. Phys. Lett.
362 (56): 36264. Bibcode:2002CPL...362..362M.
doi:10.1016/S0009-2614(02)00919-3.
[6] Goudsmit, S. A.; Richards, Paul I. (1964). The
Order of Electron Shells in Ionized Atoms (PDF).
Proc. Natl. Acad. Sci. 51 (4): 664671 (with
correction on p 906). Bibcode:1964PNAS...51..664G.
doi:10.1073/pnas.51.4.664 .
[7] Wong, D. Pan (1979).
Theoretical justicaJ. Chem.
Ed.
56
tion of Madelungs rule.
(11):
714718.
Bibcode:1979JChEd..56..714W.
doi:10.1021/ed056p714.
[8] Scerri, Eric (2013). The Trouble With the Aufbau Principle. Education in Chemistry. 50 (11): 2426.

5 Further reading
Image: Understanding order of shell lling
Boeyens, J. C. A.: Chemistry from First Principles.
Berlin: Springer Science 2008, ISBN 978-1-40208546-8

3
Ostrovsky, V.N. (2005). On Recent Discussion
Concerning Quantum Justication of the Periodic
Table of the Elements. Foundations of Chemistry.
7 (3): 23539. doi:10.1007/s10698-005-2141-y.
Kitagawara, Y.; Barut, A.O. (1984). On the dynamical symmetry of the periodic table. II. Modied Demkov-Ostrovsky atomic model. J. Phys. B.
17 (21): 425159. Bibcode:1984JPhB...17.4251K.
doi:10.1088/0022-3700/17/21/013.
Scerri, E.R. (2013). The Trouble with the Aufbau
Principle. Education in Chemistry: 2426.
Vanquickenborne, L. G. (1994).
Transition
Metals and the Aufbau Principle (PDF).
Journal of Chemical Education.
71 (6):
469471.
Bibcode:1994JChEd..71..469V.
doi:10.1021/ed071p469.

External links
Electron Congurations, the Aufbau Principle, Degenerate Orbitals, and Hunds Rule from Purdue
University

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