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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
fore 2s). In this way, the electrons of an atom, molecule, lled before those with higher
n + values. In this con-
or ion harmonize into the most stable electron congura- text, n represents the principal quantum number and
tion possible. the azimuthal quantum number; the values = 0, 1, 2, 3
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
the building-up principle or the Aufbau rule. atomic orbital, n + , which is related to the energy.[3]
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 follow-
havior 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 or-
bitals rst, before reusing orbitals occupied by other elec- The Madelung energy ordering rule applies only to neu-
tral 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 congura-
have dierent spins (1/2 and 1/2). tions that dier from those determined experimentally.[5]
Copper, chromium, and palladium are common exam-
A 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 congu-
1 Madelung energy ordering rule ration of Ar (the preceding noble gas). However the ex-
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 elec-
tronic conguration of [Ar]4s1 3d5 instead of [Ar]4s2 3d4 .
In this case, chromium has a half-full 3d shell. For pal-
ladium, the Madelung rule predicts [Kr]5s2 4d8 , but the
experimental conguration [Kr]4d10 diers in the place-
ment of two electrons.

2 History

2.1 The Aufbau principle in the new quan-


tum theory

The principle takes its name from the German, Aufbau-


prinzip, building-up principle, rather than being named
The states crossed by the same arrow have same n + value. The for a scientist. In fact, it was formulated by Niels Bohr
arrow direction indicates the order of lling states. and Wolfgang Pauli in the early 1920s, and states that:

1
2 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]

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

5d (=2)

Valence electrons
5f (=3)

5g (=4)
Wiswessers rule

In the old quantum theory, orbits with low angular momentum


(s- and p-orbitals) get closer to the nucleus. 4 References
[1] Cottingham, W. N.; Greenwood, D. A. (1986). Chapter
This was an early application of quantum mechanics to 5: Ground state properties of nuclei: the shell model.
the properties of electrons, and explained chemical prop- An introduction to nuclear physics. Cambridge University
erties in physical terms. Each added electron is subject Press. ISBN 0-521-31960-9.
to the electric eld created by the positive charge of the
atomic nucleus and the negative charge of other electrons [2] Electron Conguration. WyzAnt.
that are bound to the nucleus. Although in hydrogen there [3] Weinhold, Frank; Landis, Clark R. (2005). Valency and
is no energy dierence between orbitals with the same bonding: A Natural Bond Orbital Donor-Acceptor Perspec-
principal quantum number n, this is not true for the outer tive. Cambridge: Cambridge University Press. pp. 715
electrons of other atoms. 716. ISBN 0-521-83128-8.
In the old quantum theory prior to quantum mechan- [4] Scerri, Eric R. (1998). How Good is the
ics, electrons were supposed to occupy classical elliptical Quantum Mechanical Explanation of the Pe-
orbits. The orbits with the highest angular momentum riodic System?" (PDF). J. Chem. Ed. 75
are 'circular orbits outside the inner electrons, but or- (11): 138485. Bibcode:1998JChEd..75.1384S.
bits with low angular momentum (s- and p-orbitals) have doi:10.1021/ed075p1384 .
high orbital eccentricity, so that they get closer to the nu-
cleus and feel on average a less strongly screened nuclear [5] Meek, Terry L.; Allen, Leland C. (2002). Congura-
charge. tion 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.
2.2 The n + energy ordering rule
[6] Goudsmit, S. A.; Richards, Paul I. (1964). The
A periodic table in which each row corresponds to one Order of Electron Shells in Ionized Atoms (PDF).
value of n + was suggested by Charles Janet in 1927. Proc. Natl. Acad. Sci. 51 (4): 664671 (with
In 1936, the German physicist Erwin Madelung proposed correction on p 906). Bibcode:1964PNAS...51..664G.
his empirical rules for the order of lling atomic sub- doi:10.1073/pnas.51.4.664 .
shells, based on knowledge of atomic ground states de-
[7] Wong, D. Pan (1979). Theoretical justica-
termined by the analysis of atomic spectra, and most tion of Madelungs rule. J. Chem. Ed. 56
English-language sources therefore refer to the Madelung (11): 714718. Bibcode:1979JChEd..56..714W.
rule. Madelung may have been aware of this pattern as doi:10.1021/ed056p714.
early as 1926.[6] In 1962 the Russian agricultural chemist
V.M. Klechkowski proposed the rst theoretical expla- [8] Scerri, Eric (2013). The Trouble With the Aufbau Prin-
nation for the importance of the sum n + , based on ciple. Education in Chemistry. 50 (11): 2426.
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 5 Further reading
challenged the validity of Madelungs rule in predicting
the order of lling of atomic orbitals. For example, it has Image: Understanding order of shell lling
been claimed, not for the rst time, that in the case of the
scandium atom a 3d orbital is occupied before the occu- Boeyens, J. C. A.: Chemistry from First Principles.
pation of the 4s orbital. In addition to there being ample Berlin: Springer Science 2008, ISBN 978-1-4020-
experimental evidence to support this view, it makes the 8546-8
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 dy-
namical symmetry of the periodic table. II. Modi-
ed 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.

6 External links
Electron Congurations, the Aufbau Principle, De-
generate Orbitals, and Hunds Rule from Purdue
University
4 7 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

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