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Aufbau principle
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"Atomic build-up" redirects here. For the spread of nuclear weapons, see Nuclear proliferation.
The Aufbau principle (from the German Aufbau meaning "building up, construction": also

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Aufbau rule or building-up principle) is used to determine the electron configuration of an

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atom, molecule or ion. The principle postulates a hypothetical process in which an atom is "built

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up" by progressively adding electrons. As they are added, they assume their most stable

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conditions (electron orbitals) with respect to the nucleus and those electrons already there.

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According to the principle, electrons fill orbitals starting at the lowest available (possible) energy
levels before filling higher levels (e.g. 1s before 2s). The number of electrons that can occupy
each orbital is limited by the Pauli exclusion principle. If multiple orbitals of the same energy are

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available, Hund's rule states that unoccupied orbitals will be filled before occupied orbitals are

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reused (by electrons having different spins).

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A version of the Aufbau principle can also be used to predict the configuration of protons and
neutrons in an atomic nucleus.

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1 The Madelung energy ordering rule

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2 History

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2.1 The Aufbau principle in the old quantum theory

2.2 The n + energy ordering rule
3 See also
4 References

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5 Further reading
6 External links

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The Madelung energy ordering rule

The order in which these orbitals are

filled is given by the n + rule (also

Deutsch

known as the Madelung rule (after

Eesti

Erwin Madelung), or the Klechkowski

Espaol

rule (after Vsevolod Klechkovsky in

[edit]

some, mostly French and Russian-

Franais

speaking, countries), or the diagonal

Italiano

rule.[1] Orbitals with a lower n + value

Portugus

are filled before those with higher n +

values. In this context, n represents the

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principal quantum number and the

azimuthal quantum number; the values
= 0, 1, 2, 3 correspond to the s, p, d, and
f labels, respectively.
The rule is based on the total number of

Order in which orbitals are arranged by increasing

energy according to the Madelung rule. Each diagonal red
arrow corresponds to a different value of n + .

nodes in the atomic orbital, n + , which is

related to the energy.[2] In the case of
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equal n + values, the orbital with a lower n value is filled first. The fact that most of the ground
state configurations of neutral atoms fill orbitals following this n + , n pattern was obtained
experimentally, by reference to the spectroscopic characteristics of the elements.[3]
The Madelung energy ordering rule applies only to neutral atoms in their ground state, and even
in that case, there are several elements for which it predicts configurations that differ from those
determined experimentally.[4] Copper, chromium, and palladium are common examples of this
property. According to the Madelung rule, the 4s orbital (n + = 4 + 0 = 4) is occupied before the
3d orbital (n + = 3 + 2 = 5). The rule then predicts the configuration of 29Cu to be 1s22s22p63s2
3p64s23d9, abbreviated [Ar]4s23d9 where [Ar] denotes the configuration of Ar (the preceding
noble gas). However the experimental electronic configuration of the copper atom is [Ar]4s13d10.
By filling the 3d orbital, copper can be in a lower energy state. Similarly, chromium takes the
electronic configuration of [Ar]4s13d5 instead of [Ar]4s23d4. In this case, chromium has a half-full
3d shell. For palladium, the Madelung rule predicts [Kr]5s24d8, but the experimental configuration
[Kr]4d10 differs in the placement of two electrons.

History

[edit]

The Aufbau principle in the old quantum theory [edit]

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:

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The orbitals of lower energy are filled in

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first with the electrons and only then the

orbitals of high energy are filled.

This was an early application of quantum mechanics to the

In the old quantum theory, orbits

with low angular momentum (s- and porbitals) get closer to the nucleus.

properties of electrons, and explained chemical properties

in physical terms. Each added electron is subject to the electric field 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 difference 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.

The n + energy ordering rule [edit]

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 filling 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.[5] In 1962 the Russian
agricultural chemist V.M. Klechkowski proposed the first theoretical explanation for the importance
of the sum n + , based on the statistical ThomasFermi model of the atom.[6] Many French- and
Russian-language sources therefore refer to the Klechkowski rule.

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See also

[edit]

Electron configuration
Valence electrons
Wiswesser's rule

References

[edit]

1. ^ http://www.wyzant.com/resources/lessons/science/chemistry/electron_configuration
2. ^ Weinhold, Frank; Landis, Clark R. (2005). Valency and bonding: A Natural Bond Orbital DonorAcceptor Perspective. Cambridge: Cambridge University Press. pp. 71516. ISBN 0-521-83128-8.
3. ^ Scerri, Eric R. (1998). "How Good is the Quantum Mechanical Explanation of the Periodic
System?"

. J. Chem. Ed. 75 (11): 138485. Bibcode:1998JChEd..75.1384S

doi:10.1021/ed075p1384 .
4. ^ Meek, Terry L.; Allen, Leland C. (2002). "Configuration irregularities: deviations from the Madelung
rule and inversion of orbital energy levels"
Bibcode:2002CPL...362..362M

. Chem. Phys. Lett. 362 (56): 36264.

. doi:10.1016/S0009-2614(02)00919-3 .

5. ^ Goudsmit, S. A.; Richards, Paul I. (1964). "The Order of Electron Shells in Ionized Atoms"

Proc. Natl. Acad. Sci. 51 (4): 664671 (with correction on p 906). Bibcode:1964PNAS...51..664G .
doi:10.1073/pnas.51.4.664 .
6. ^ Wong, D. Pan (1979). "Theoretical justification of Madelung's rule"
18. Bibcode:1979JChEd..56..714W

Further reading

. J. Chem. Ed. 56 (11): 714

. doi:10.1021/ed056p714 .

[edit]

Image: Understanding order of shell filling

Boeyens, J. C. A.: Chemistry from First Principles. Berlin: Springer Science 2008, ISBN 978-14020-8546-8
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Ostrovsky, V.N. (2005). "On Recent Discussion Concerning Quantum Justification of the
Periodic Table of the Elements"

. Foundations of Chemistry 7 (3): 23539.

doi:10.1007/s10698-005-2141-y . Abstract

Kitagawara, Y.; Barut, A.O. (1984). "On the dynamical symmetry of the periodic table. II.
Modified Demkov-Ostrovsky atomic model"

. J. Phys. B: At. Mol. Phys. 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
(November): 2426.
Vanquickenborne, L. G. (1994). "Transition Metals and the Aufbau Principle"

. Journal of

Chemical Education 71 (6): 469471. Bibcode:1994JChEd..71..469V .

doi:10.1021/ed071p469 .

External links

[edit]

Electron Configurations, the Aufbau Principle, Degenerate Orbitals, and Hund's Rule
Categories: Atomic physics

This page w as last modified on 30 July 2014 at 15:37.

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