
In
atomic physics
Atomic physics is the field of physics that studies atoms as an isolated system of electrons and an atomic nucleus. Atomic physics typically refers to the study of atomic structure and the interaction between atoms. It is primarily concerned wit ...
and
quantum chemistry
Quantum chemistry, also called molecular quantum mechanics, is a branch of physical chemistry focused on the application of quantum mechanics to chemical systems, particularly towards the quantum-mechanical calculation of electronic contributions ...
, the electron configuration is the
distribution of
electron
The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary charge, elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up qua ...
s of an
atom
Atoms are the basic particles of the chemical elements. An atom consists of a atomic nucleus, nucleus of protons and generally neutrons, surrounded by an electromagnetically bound swarm of electrons. The chemical elements are distinguished fr ...
or
molecule
A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
(or other physical structure) in
atomic or
molecular orbitals.
For example, the electron configuration of the
neon
Neon is a chemical element; it has symbol Ne and atomic number 10. It is the second noble gas in the periodic table. Neon is a colorless, odorless, inert monatomic gas under standard conditions, with approximately two-thirds the density of ...
atom is , meaning that the 1s, 2s, and 2p
subshells are occupied by two, two, and six electrons, respectively.
Electronic configurations describe each electron as moving independently in an
orbital, in an average
field created by the
nuclei and all the other electrons. Mathematically, configurations are described by
Slater determinants or
configuration state functions.
According to the laws of
quantum mechanics
Quantum mechanics is the fundamental physical Scientific theory, theory that describes the behavior of matter and of light; its unusual characteristics typically occur at and below the scale of atoms. Reprinted, Addison-Wesley, 1989, It is ...
, a
level of energy is associated with each electron configuration. In 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
A photon () is an elementary particle that is a quantum of the electromagnetic field, including electromagnetic radiation such as light and radio waves, and the force carrier for the electromagnetic force. Photons are massless particles that can ...
.
Knowledge of the electron configuration of different atoms is useful in understanding the structure of the
periodic table of elements, for describing the
chemical bond
A chemical bond is the association of atoms or ions to form molecules, crystals, and other structures. The bond may result from the electrostatic force between oppositely charged ions as in ionic bonds or through the sharing of electrons a ...
s that hold atoms together, and in understanding the
chemical formula
A chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, such as pare ...
s of compounds and the
geometries of molecules. In bulk materials, this same idea helps explain the peculiar properties of
lasers
A laser is a device that emits light through a process of optical amplification based on the stimulated emission of electromagnetic radiation. The word ''laser'' originated as an acronym for light amplification by stimulated emission of radi ...
and
semiconductors.
Shells and subshells
Electron configuration was first conceived under the
Bohr model
In atomic physics, the Bohr model or Rutherford–Bohr model was a model of the atom that incorporated some early quantum concepts. Developed from 1911 to 1918 by Niels Bohr and building on Ernest Rutherford's nuclear Rutherford model, model, i ...
of the
atom
Atoms are the basic particles of the chemical elements. An atom consists of a atomic nucleus, nucleus of protons and generally neutrons, surrounded by an electromagnetically bound swarm of electrons. The chemical elements are distinguished fr ...
, and it is still common to speak of
shells and subshells despite the advances in understanding of the
quantum-mechanical nature of
electrons
The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary charge, elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up qua ...
.
An
electron shell is the
set of
allowed states that share the same
principal quantum number, ''n'', that electrons may occupy. In each
term of an electron configuration, ''n'' is the
positive integer that precedes each
orbital letter (e.g.
helium
Helium (from ) is a chemical element; it has chemical symbol, symbol He and atomic number 2. It is a colorless, odorless, non-toxic, inert gas, inert, monatomic gas and the first in the noble gas group in the periodic table. Its boiling point is ...
's electron configuration is 1s
2, therefore ''n'' = 1, and the orbital contains two electrons). An atom's ''n''th electron shell can accommodate 2''n''
2 electrons. For example, the first shell can accommodate two electrons, the second shell eight electrons, the third shell eighteen, and so on. The factor of two arises because the number of allowed states doubles with each successive shell due to
electron spin—each atomic orbital admits up to two otherwise identical electrons with opposite spin, one with a spin + (usually denoted by an up-arrow) and one with a spin of − (with a down-arrow).
A
subshell is the set of states defined by a common
azimuthal quantum number, , within a shell. The value of is in the range from 0 to ''n'' − 1. The values = 0, 1, 2, 3 correspond to the s, p, d, and f labels, respectively. For example, the 3d subshell has ''n'' = 3 and = 2. 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 number
In quantum physics and chemistry, quantum numbers are quantities that characterize the possible states of the system.
To fully specify the state of the electron in a hydrogen atom, four quantum numbers are needed. The traditional set of quantu ...
s.
Exhaustive technical details about the complete quantum mechanical theory of atomic spectra and structure can be found and studied in the basic book of Robert D. Cowan.
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
subshell labels (e.g. for
phosphorus
Phosphorus is a chemical element; it has Chemical symbol, symbol P and atomic number 15. All elemental forms of phosphorus are highly Reactivity (chemistry), reactive and are therefore never found in nature. They can nevertheless be prepared ar ...
the sequence 1s, 2s, 2p, 3s, 3p) with the number of electrons assigned to each subshell placed as a superscript. For example,
hydrogen
Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
has one electron in the s-orbital of the first shell, so its configuration is written 1s
1.
Lithium
Lithium (from , , ) is a chemical element; it has chemical symbol, symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard temperature and pressure, standard conditions, it is the least dense metal and the ...
has two electrons in the 1s-subshell and one in the (higher-energy) 2s-subshell, so its configuration is written 1s
2 2s
1 (pronounced "one-s-two, two-s-one").
Phosphorus
Phosphorus is a chemical element; it has Chemical symbol, symbol P and atomic number 15. All elemental forms of phosphorus are highly Reactivity (chemistry), reactive and are therefore never found in nature. They can nevertheless be prepared ar ...
(
atomic number
The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of its atomic nucleus. For ordinary nuclei composed of protons and neutrons, this is equal to the proton number (''n''p) or the number of pro ...
15) is as follows: 1s
2 2s
2 2p
6 3s
2 3p
3.
For atoms with many electrons, this notation can become lengthy and so an abbreviated notation is used. The electron configuration can be visualized as the
core electrons, equivalent to the
noble gas
The noble gases (historically the inert gases, sometimes referred to as aerogens) are the members of Group (periodic table), group 18 of the periodic table: helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn) and, in some ...
of the preceding
period, and the
valence electrons: each element in a period differs only by the last few subshells. Phosphorus, for instance, is in the third period. It differs from the second-period
neon
Neon is a chemical element; it has symbol Ne and atomic number 10. It is the second noble gas in the periodic table. Neon is a colorless, odorless, inert monatomic gas under standard conditions, with approximately two-thirds the density of ...
, whose configuration is 1s
2 2s
2 2p
6, only by the presence of a third shell. The portion of its configuration that is equivalent to neon is abbreviated as
e allowing the configuration of phosphorus to be written as
enbsp;3s
2 3p
3 rather than writing out the details of the configuration of neon explicitly. 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
Titanium is a chemical element; it has symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in ...
ground state can be written as either
rnbsp;4s
2 3d
2 or
rnbsp;3d
2 4s
2. 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 Ti
4+, Ti
3+, Ti
2+, Ti
+, Ti.
The superscript 1 for a singly occupied subshell is not compulsory; for example
aluminium
Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
may be written as either
enbsp;3s
2 3p
1 or
enbsp;3s
2 3p. In atoms where a subshell is unoccupied despite higher subshells being occupied (as is the case in some ions, as well as certain neutral atoms shown to deviate from the
Madelung rule), the empty subshell is either denoted with a superscript 0 or left out altogether. For example, neutral
palladium may be written as either or simply , and the
lanthanum(III) ion may be written as either or simply
e
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
The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
(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, , of 0, 1, 2 or 3 respectively. After f, the sequence continues alphabetically g, h, i... ( = 4, 5, 6...), skipping j, although orbitals of these types are rarely required.
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 of 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
In quantum mechanics
Quantum mechanics is the fundamental physical Scientific theory, theory that describes the behavior of matter and of light; its unusual characteristics typically occur at and below the scale of atoms. Reprinted, Add ...
.
As an example, the ground state configuration of the
sodium
Sodium is a chemical element; it has Symbol (chemistry), symbol Na (from Neo-Latin ) and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the peri ...
atom is 1s
2 2s
2 2p
6 3s
1, as deduced from the Aufbau principle (see below). The first excited state is obtained by promoting a 3s electron to the 3p subshell, to obtain the
1s
2 2s
2 2p
6 3p
1 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
photon
A photon () is an elementary particle that is a quantum of the electromagnetic field, including electromagnetic radiation such as light and radio waves, and the force carrier for the electromagnetic force. Photons are massless particles that can ...
s of visible or
ultraviolet
Ultraviolet radiation, also known as simply UV, is electromagnetic radiation of wavelengths of 10–400 nanometers, shorter than that of visible light, but longer than X-rays. UV radiation is present in sunlight and constitutes about 10% of ...
light. The excitation of
core electrons is possible, but requires much higher energies, generally corresponding to
X-ray
An X-ray (also known in many languages as Röntgen radiation) is a form of high-energy electromagnetic radiation with a wavelength shorter than those of ultraviolet rays and longer than those of gamma rays. Roughly, X-rays have a wavelength ran ...
photons. This would be the case for example to excite a 2p electron of sodium to the 3s level and form the excited 1s
2 2s
2 2p
5 3s
2 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
Irving Langmuir was the first to propose in his 1919 article "The Arrangement of Electrons in Atoms and Molecules" in which, building on
Gilbert N. Lewis's
cubical atom theory and
Walther Kossel's chemical bonding theory, he outlined his "concentric theory of atomic structure". Langmuir had developed his work on electron atomic structure from other chemists as is shown in the development of the
History of the periodic table and the
Octet rule
The octet rule is a chemical rule of thumb that reflects the theory that main-group elements tend to bond in such a way that each atom has eight electrons in its valence shell, giving it the same electronic configuration as a noble gas. The ru ...
.
Niels Bohr
Niels Henrik David Bohr (, ; ; 7 October 1885 – 18 November 1962) was a Danish theoretical physicist who made foundational contributions to understanding atomic structure and old quantum theory, quantum theory, for which he received the No ...
(1923) incorporated Langmuir's model that the
periodicity in the properties of the elements might be explained by the electronic structure of the atom.
His proposals were based on the then current
Bohr model
In atomic physics, the Bohr model or Rutherford–Bohr model was a model of the atom that incorporated some early quantum concepts. Developed from 1911 to 1918 by Niels Bohr and building on Ernest Rutherford's nuclear Rutherford model, model, i ...
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
Sulfur ( American spelling and the preferred IUPAC name) or sulphur ( Commonwealth spelling) is a chemical element; it has symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms ...
was given as 2.4.4.6 instead of 1s
2 2s
2 2p
6 3s
2 3p
4 (2.8.6). Bohr used 4 and 6 following
Alfred Werner's 1893 paper. In fact, the chemists accepted the concept of atoms long before the physicists. Langmuir began his paper referenced above by saying,
«…The problem of the structure of atoms has been attacked mainly by physicists who have given little consideration to the chemical properties which must ultimately be explained by a theory of atomic structure. The vast store of knowledge of chemical properties and relationships, such as is summarized by the Periodic Table, should serve as a better foundation for a theory of atomic structure than the relatively meager experimental data along purely physical lines... These electrons arrange themselves in a series of concentric shells, the first shell containing two electrons, while all other shells tend to hold eight.…»
The valence electrons in the atom were described by
Richard Abegg in 1904.
In 1924,
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. However neither Bohr's system nor Stoner's could correctly describe the changes in
atomic spectra in a
magnetic field
A magnetic field (sometimes called B-field) is a physical field that describes the magnetic influence on moving electric charges, electric currents, and magnetic materials. A moving charge in a magnetic field experiences a force perpendicular ...
(the
Zeeman effect).
Bohr was well aware of this shortcoming (and others), and had written to his friend
Wolfgang Pauli in 1923 to ask for his help in saving quantum theory (the system now known as "
old quantum theory"). Pauli hypothesized successfully that the Zeeman effect can be explained as depending only on the response of the outermost (i.e., valence) electrons of the atom. Pauli 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):
The
Schrödinger equation
The Schrödinger equation is a partial differential equation that governs the wave function of a non-relativistic quantum-mechanical system. Its discovery was a significant landmark in the development of quantum mechanics. It is named after E ...
, published in 1926, gave three of the four quantum numbers as a direct consequence of its solution for the hydrogen atom: 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),
see below) for the order in which atomic orbitals are filled with electrons.
Atoms: Aufbau principle and Madelung rule
The
aufbau principle
In atomic physics and quantum chemistry, the Aufbau principle (, from ), also called the Aufbau rule, states that in the ground state of an atom or ion, electrons first fill Electron shell#Subshells, subshells of the lowest available energy, the ...
(from the
German ''Aufbau'', "building up, construction") 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 subshells are filled before electrons are placed in higher-energy orbitals.''

The principle works very well (for the ground states of the atoms) for the known 118 elements, although it is sometimes slightly wrong. 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,
and later given a theoretical justification by
V. M. Klechkowski:
#
Subshells are filled in the order of increasing ''n'' + .
# Where two subshells have the same value of ''n'' + , 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, , 6f, 7d, 8p, and 9s)
In this list the subshells in parentheses are not occupied in the ground state of the heaviest atom now known (
Og, ''Z'' = 118).
The aufbau principle can be applied, in a modified form, to the
proton
A proton is a stable subatomic particle, symbol , Hydron (chemistry), H+, or 1H+ with a positive electric charge of +1 ''e'' (elementary charge). Its mass is slightly less than the mass of a neutron and approximately times the mass of an e ...
s and
neutron
The neutron is a subatomic particle, symbol or , that has no electric charge, and a mass slightly greater than that of a proton. The Discovery of the neutron, neutron was discovered by James Chadwick in 1932, leading to the discovery of nucle ...
s in the
atomic nucleus
The atomic nucleus is the small, dense region consisting of protons and neutrons at the center of an atom, discovered in 1911 by Ernest Rutherford at the Department_of_Physics_and_Astronomy,_University_of_Manchester , University of Manchester ...
, as in the
shell model of
nuclear physics
Nuclear physics is the field of physics that studies atomic nuclei and their constituents and interactions, in addition to the study of other forms of nuclear matter.
Nuclear physics should not be confused with atomic physics, which studies th ...
and
nuclear chemistry.
Periodic table
The form of the
periodic table
The periodic table, also known as the periodic table of the elements, is an ordered arrangement of the chemical elements into rows (" periods") and columns (" groups"). It is an icon of chemistry and is widely used in physics and other s ...
is closely related to the atomic electron configuration for each element. For example, all the elements of
group 2 (the table's second column) have an electron configuration of
nbsp;''n''s (where
is a
noble gas
The noble gases (historically the inert gases, sometimes referred to as aerogens) are the members of Group (periodic table), group 18 of the periodic table: helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn) and, in some ...
configuration), and have notable similarities in their chemical properties. The periodicity of the periodic table in terms of
periodic table blocks is due to the number of electrons (2, 6, 10, and 14) needed to fill s, p, d, and f subshells. These blocks appear as the rectangular sections of the periodic table. The single exception is
helium
Helium (from ) is a chemical element; it has chemical symbol, symbol He and atomic number 2. It is a colorless, odorless, non-toxic, inert gas, inert, monatomic gas and the first in the noble gas group in the periodic table. Its boiling point is ...
, which despite being an s-block atom is conventionally placed with the other
noble gas
The noble gases (historically the inert gases, sometimes referred to as aerogens) are the members of Group (periodic table), group 18 of the periodic table: helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn) and, in some ...
ses in the p-block due to its chemical inertness, a consequence of its full outer shell (though there is discussion in the contemporary literature on whether this exception should be retained).
The electrons in the
valence (outermost) shell largely determine each element's
chemical properties
A chemical property is any of a material property, material's properties that becomes evident during, or after, a chemical reaction; that is, any attribute that can be established only by changing a substance's chemical substance, chemical identit ...
. The similarities in the chemical properties were remarked on more than a century before the idea of electron configuration.
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 (although there are mathematical approximations available, such as the
Hartree–Fock 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 level
A quantum mechanics, quantum mechanical system or particle that is bound state, bound—that is, confined spatially—can only take on certain discrete values of energy, called energy levels. This contrasts with classical mechanics, classical pa ...
s are slightly split by the magnetic field of the nucleus, and by the
quantum electrodynamic effects of the
Lamb shift
In physics, the Lamb shift, named after Willis Lamb, is an anomalous difference in energy between two electron orbitals in a hydrogen atom. The difference was not predicted by theory and it cannot be derived from the Dirac equation, which pre ...
.)
Ionization of the transition metals
The naïve application of the aufbau principle leads to a well-known
paradox (or apparent paradox) in the basic chemistry of the
transition metals.
Potassium
Potassium is a chemical element; it has Symbol (chemistry), symbol K (from Neo-Latin ) and atomic number19. It is a silvery white metal that is soft enough to easily cut with a knife. Potassium metal reacts rapidly with atmospheric oxygen to ...
and
calcium
Calcium is a chemical element; it has symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to it ...
appear in the periodic table before the transition metals, and have electron configurations
rnbsp;4s and
rnbsp;4s 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'' + = 4 (''n'' = 4, = 0) while the 3d-orbital has ''n'' + = 5 (''n'' = 3, = 2). After calcium, most neutral atoms in the first series of transition metals (
scandium
Scandium is a chemical element; it has Symbol (chemistry), symbol Sc and atomic number 21. It is a silvery-white metallic d-block, d-block element. Historically, it has been classified as a rare-earth element, together with yttrium and the lantha ...
through
zinc
Zinc is a chemical element; it has symbol Zn and atomic number 30. It is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic tabl ...
) have configurations with two 4s electrons, but there are two exceptions.
Chromium
Chromium is a chemical element; it has Symbol (chemistry), symbol Cr and atomic number 24. It is the first element in Group 6 element, group 6. It is a steely-grey, Luster (mineralogy), lustrous, hard, and brittle transition metal.
Chromium ...
and
copper
Copper is a chemical element; it has symbol Cu (from Latin ) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkish-orang ...
have electron configurations
rnbsp;3d 4s and
rnbsp;3d 4s respectively, 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". However, this is not supported by the facts, as tungsten (W) has a Madelung-following d s configuration and not d s, and niobium (Nb) has an anomalous d s configuration that does not give it a half-filled or completely filled subshell.
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. 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 Fe
4+, Fe
3+, Fe
2+, 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 3p-orbital, as it does in hydrogen, yet it clearly does not. There is no special reason why the Fe 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 the
Hartree–Fock method of atomic structure calculation. More recently Scerri has argued that contrary to what is stated in the vast majority of sources including the title of his previous article on the subject, 3d orbitals rather than 4s are in fact preferentially occupied.
In chemical environments, configurations can change even more: Th
3+ as a bare ion has a configuration of [Rn] 5f
1, yet in most Th
III compounds the thorium atom has a 6d
1 configuration instead. Mostly, what is present is rather a superposition of various configurations.
For instance, copper metal is poorly described by either an
rnbsp;3d 4s or an
rnbsp;3d 4s configuration, but is rather well described as a 90% contribution of the first and a 10% contribution of the second. Indeed, visible light is already enough to excite electrons in most transition metals, and they often continuously "flow" through different configurations when that happens (copper and its group are an exception).
Similar ion-like 3d 4s 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 3d 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 Aufbau principle#Madelung energy ordering rule, Madelung's rule among the heavier elements, and as atomic number increases it becomes more and more difficult to find simple explanations such as the stability of half-filled subshells. It is possible to predict most of the exceptions by Hartree–Fock calculations, which are an approximate method for taking account of the effect of the other electrons on orbital energies. Qualitatively, for example, the 4d elements have the greatest concentration of Madelung anomalies, because the 4d–5s gap is larger than the 3d–4s and 5d–6s gaps.
For the heavier elements, it is also necessary to take account of the Relativistic quantum chemistry, 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 tend to decrease the energy of the s-orbitals in relation to the other atomic orbitals. This is the reason why the 6d elements are predicted to have no Madelung anomalies apart from lawrencium (for which relativistic effects stabilise the p
1/2 orbital as well and cause its occupancy in the ground state), as relativity intervenes to make the 7s orbitals lower in energy than the 6d ones.
The table below shows the configurations of the f-block (green) and d-block (blue) atoms. It 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). However this also depends on the charge: a
calcium
Calcium is a chemical element; it has symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to it ...
atom has 4s lower in energy than 3d, but a Ca
2+ cation has 3d lower in energy than 4s. In practice the configurations predicted by the Madelung rule are at least close to the ground state even in these anomalous cases. The empty f orbitals in lanthanum, actinium, and thorium contribute to chemical bonding,
as do the empty p orbitals in transition metals.
Vacant s, d, and f orbitals have been shown explicitly, as is occasionally done, to emphasise the filling order and to clarify that even orbitals unoccupied in the ground state (e.g. lanthanum 4f or
palladium 5s) may be occupied and bonding in chemical compounds. (The same is also true for the p-orbitals, which are not explicitly shown because they are only actually occupied for lawrencium in gas-phase ground states.)
The various anomalies describe the free atoms and do not necessarily predict chemical behavior. Thus for example neodymium typically forms the +3 oxidation state, despite its configuration that if interpreted naïvely would suggest a more stable +2 oxidation state corresponding to losing only the 6s electrons. Contrariwise, uranium as is not very stable in the +3 oxidation state either, preferring +4 and +6.
The electron-shell configuration of elements beyond hassium has not yet been empirically verified, but they are expected to follow Madelung's rule without exceptions until unbinilium, element 120. Unbiunium, Element 121 should have the anomalous configuration , having a p rather than a g electron. Electron configurations beyond this are tentative and predictions differ between models, but Madelung's rule is expected to break down due to the closeness in energy of the , 6f, 7d, and 8p
1/2 orbitals.
That said, the filling sequence 8s, , 6f, 7d, 8p is predicted to hold approximately, with perturbations due to the huge spin-orbit splitting of the 8p and 9p shells, and the huge relativistic stabilisation of the 9s shell.
Open and closed shells
In the context of atomic orbitals, an open shell is a valence shell which is not completely filled with
electron
The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary charge, elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up qua ...
s or that has not given all of its valence electrons through
chemical bond
A chemical bond is the association of atoms or ions to form molecules, crystals, and other structures. The bond may result from the electrostatic force between oppositely charged ions as in ionic bonds or through the sharing of electrons a ...
s with other
atom
Atoms are the basic particles of the chemical elements. An atom consists of a atomic nucleus, nucleus of protons and generally neutrons, surrounded by an electromagnetically bound swarm of electrons. The chemical elements are distinguished fr ...
s or
molecule
A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
s during a chemical reaction. Conversely a closed shell is obtained with a completely filled valence shell. This configuration is very Stable nuclide, stable.
For molecules, "open shell" signifies that there are Unpaired electron, unpaired electrons. In
molecular orbital theory, this leads to molecular orbitals that are singly occupied. In computational chemistry implementations of molecular orbital theory, open-shell molecules have to be handled by either the restricted open-shell Hartree–Fock method or the unrestricted Hartree–Fock method. Conversely a closed-shell configuration corresponds to a state where all
molecular orbitals are either doubly occupied or empty (a diradical, singlet state). Open shell molecules are more difficult to study computationally.
Noble gas configuration
Noble gas configuration is the electron configuration of Noble gas, noble gases. The basis of all chemical reactions is the tendency of chemical elements to acquire Stable nuclide, stability. Main-group element, Main-group atoms generally obey the octet rule, while
transition metals generally obey the 18-electron rule. The
noble gas
The noble gases (historically the inert gases, sometimes referred to as aerogens) are the members of Group (periodic table), group 18 of the periodic table: helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn) and, in some ...
es (Helium, He, Neon, Ne, Argon, Ar, Krypton, Kr, Xenon, Xe, Radon, Rn) are less Electrical reactance, reactive than other Chemical element, elements because they already have a noble gas configuration. Oganesson#Predicted compounds, Oganesson is predicted to be more reactive due to Relativistic quantum chemistry, relativistic effects for heavy atoms.
:
Every system has the tendency to acquire the state of stability or a state of minimum energy, and so chemical elements take part in chemical reactions to acquire a stable electronic configuration similar to that of its nearest
noble gas
The noble gases (historically the inert gases, sometimes referred to as aerogens) are the members of Group (periodic table), group 18 of the periodic table: helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn) and, in some ...
. An example of this tendency is two
hydrogen
Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
(H) atoms reacting with one oxygen (O) atom to form water (H
2O). Neutral atomic hydrogen has one electron in its Valence electron, valence shell, and on formation of water it acquires a share of a second electron coming from oxygen, so that its configuration is similar to that of its nearest noble gas
helium
Helium (from ) is a chemical element; it has chemical symbol, symbol He and atomic number 2. It is a colorless, odorless, non-toxic, inert gas, inert, monatomic gas and the first in the noble gas group in the periodic table. Its boiling point is ...
(He) with two electrons in its valence shell. Similarly, neutral atomic oxygen has six electrons in its valence shell, and acquires a share of two electrons from the two hydrogen atoms, so that its configuration is similar to that of its nearest noble gas
neon
Neon is a chemical element; it has symbol Ne and atomic number 10. It is the second noble gas in the periodic table. Neon is a colorless, odorless, inert monatomic gas under standard conditions, with approximately two-thirds the density of ...
with eight electrons in its valence shell.
Electron configuration in molecules
Electron configuration in molecules is more complex than the electron configuration of atoms, as each
molecule
A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
has a different Molecular orbital, orbital structure. The
molecular orbitals are labelled according to their Molecular symmetry, symmetry, rather than the atomic orbital labels used for Atom, atoms and Monatomic ion, monatomic ions; hence, the electron configuration of the Oxygen#Allotropes, dioxygen molecule, O, is written 1σ 1σ 2σ 2σ 3σ 1π 1π,
[Miessler G.L. and Tarr D.A. ''Inorganic Chemistry'' (2nd ed., Prentice Hall 1999) p.118 ] or equivalently 1σ 1σ 2σ 2σ 1π 3σ 1π.
The term 1π represents the two
electrons
The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary charge, elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up qua ...
in the two Degenerate energy levels, degenerate π*-orbitals (Antibonding molecular orbital, antibonding). From Hund's rules, these electrons have parallel Electron magnetic moment, 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
A photon () is an elementary particle that is a quantum of the electromagnetic field, including electromagnetic radiation such as light and radio waves, and the force carrier for the electromagnetic force. Photons are massless particles that can ...
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
A chemical property is any of a material property, material's properties that becomes evident during, or after, a chemical reaction; that is, any attribute that can be established only by changing a substance's chemical substance, chemical identit ...
, in both Inorganic chemistry, inorganic and organic chemistry. In effect, electron configurations, along with some simplified forms of molecular orbital theory, have become the modern equivalent of the valence (chemistry), valence concept, describing the number and type of Chemical bond, chemical bonds that an
atom
Atoms are the basic particles of the chemical elements. An atom consists of a atomic nucleus, nucleus of protons and generally neutrons, surrounded by an electromagnetically bound swarm of electrons. The chemical elements are distinguished fr ...
can be expected to form.
This approach is taken further in computational chemistry, which typically attempts to make Quantitative analysis (chemistry), 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 (chemistry), basis set of Atomic orbital, 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 Computational chemistry#Methods, methods in computational chemistry rely on electron configuration: density functional theory (DFT) is an important example of a method that discards the model.
For Atom, atoms or Molecule, molecules with more than one
electron
The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary charge, elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up qua ...
, the motion of electrons are Electron correlation, 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 precisely associating a certain energy level with any single configuration is not possible. 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 level, energy levels available to an atom. Term symbols can be calculated for any electron configuration, not just the Ground state, ground-state 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.
See also
* Born–Oppenheimer approximation
* d electron count
* Electron configurations of the elements (data page)
* Extended periodic table – discusses the limits of the periodic table
* Group (periodic table)
* HOMO/LUMO
* Molecular term symbol
*
Octet rule
The octet rule is a chemical rule of thumb that reflects the theory that main-group elements tend to bond in such a way that each atom has eight electrons in its valence shell, giving it the same electronic configuration as a noble gas. The ru ...
* Periodic table (electron configurations)
* Spherical harmonics
* Unpaired electron
* Valence shell
Notes
References
External links
What does an atom look like? Configuration in 3D
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Atomic physics
Chemical properties
Electron states
Molecular physics
Quantum chemistry
Theoretical chemistry