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Electron configuration

Electron atomic and molecular orbitals In atomic physics and quantum chemistry, electron configuration is the arrangement of electrons of an atom, a molecule, or other physical structure.[1] It concerns the way electrons can be distributed in the orbitals of the given system (atomic or molecular for instance . !i"e other elementary particles, the electron is sub#ect to the laws of quantum mechanics, and e$hibits both particle%li"e and wave%li"e nature. &ormally, the quantum state of a particular electron is defined by its wave function, a comple$%valued function of space and time. 'ccording to the (openhagen interpretation of quantum mechanics, the position of a particular electron is not well defined until an act of measurement causes it to be detected. )he probability that the act of measurement will detect the electron at a particular point in space is proportional to the square of the absolute value of the wavefunction at that point. 'n energy is associated with each electron configuration and, upon certain conditions, electrons are able to move from one orbital to another by emission or absorption of a quantum of energy, in the form of a photon. *nowledge of the electron configuration of different atoms is useful in understanding the structure of the periodic table of elements. )he concept is also useful for describing the chemical bonds that hold atoms together. In bul" materials this same idea helps e$plain the peculiar properties of lasers and semiconductors.

Shells and subshells

+ee also, Electron shell

Electron configuration table Electron configuration was first conceived of under the -ohr model of the atom, and it is still common to spea" of shells and subshells despite the advances in understanding of the quantum%mechanical nature of electrons. 'n electron shell is the set of allowed states electrons may occupy which share the same principal quantum number, n (the number before the letter in the orbital label . 'n atom.s nth electron shell can accommodate /n/ electrons, e.g. the first shell can accommodate / electrons, the second shell 0 electrons, and the third shell 10 electrons. )he factor of two arises because the allowed states are doubled due to electron spin1each atomic orbital admits up to two otherwise identical electrons with opposite spin, one with a spin 213/ (usually noted by an up%arrow and one with a spin %13/ (with a down%arrow . ' subshell is the set of states defined by a common a4imuthal quantum number, l, within a shell. )he values l 5 6, 1, /, 7 correspond to the s, p, d, and f labels, respectively. )he ma$imum number of electrons which can be placed in a subshell is given by /(/l 2 1 . )his gives two electrons in an s subshell, si$ electrons in a p subshell, ten electrons in a d subshell and fourteen electrons in an f subshell. )he numbers of electrons that can occupy each shell and each subshell arise from the equations of quantum mechanics,[/] in particular the 8auli e$clusion principle, which states that no two electrons in the same atom can have the same values of the four quantum numbers.[7]

[edit] Notation
+ee also, 'tomic orbital 8hysicists and chemists use a standard notation to indicate the electron configurations of atoms and molecules. &or atoms, the notation consists of a sequence of atomic orbital labels (e.g. for phosphorus the sequence 1s, /s, /p, 7s, 7p with the number of electrons assigned to each orbital (or set of orbitals sharing the same label placed as a superscript. &or e$ample, hydrogen has one electron in the s%orbital of the first shell, so its

configuration is written 1s1. !ithium has two electrons in the 1s%subshell and one in the (higher%energy /s%subshell, so its configuration is written 1s/ /s1 (pronounced 9one%s% two, two%s%one9 . 8hosphorus (atomic number 1: , is as follows, 1s/ /s/ /p; 7s/ 7p7. &or 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. 8hosphorus, for instance, differs from neon (1s/ /s/ /p; only by the presence of a third shell. )hus, the electron configuration of neon is pulled out, and phosphorus is written as follows, [<e] 7s/ 7p7. )his convention is useful as it is the electrons in the outermost shell which most determine the chemistry of the element. )he order of writing the orbitals is not completely fi$ed, some sources group all orbitals with the same value of n together, while other sources (as here follow the order given by =adelung.s rule. >ence the electron configuration of iron can be written as ['r] 7d; ?s/ ("eeping the 7d%electrons with the 7s% and 7p%electrons which are implied by the configuration of argon or as ['r] ?s/ 7d; (following the 'ufbau principle, see below . )he superscript 1 for a singly%occupied orbital is not compulsory. [?] It is quite common to see the letters of the orbital labels (s, p, d, f written in an italic or slanting typeface, although the International @nion of 8ure and 'pplied (hemistry (I@8'( recommends a normal typeface (as used here . )he choice of letters originates from a now%obsolete system of categori4ing spectral lines as 9sharp9, 9principal9, 9diffuse9 and 9fine9, based on their observed fine structure, their modern usage indicates orbitals with an a4imuthal quantum number, l, of 6, 1, / or 7 respectively. 'fter 9f9, the sequence continues alphabetically 9g9, 9h9, 9i9... (l 5 ?, :, ;... , s"ipping 9#9, although orbitals of these types are rarely required. )he electron configurations of molecules are written in a similar way, e$cept that molecular orbital labels are used instead of atomic orbital labels (see below .

[edit] Energy ground state and excited states

)he energy associated to an electron is that of its orbital. )he energy of a configuration is often appro$imated as the sum of the energy of each electron, neglecting the electron% electron interactions. )he configuration that corresponds to the lowest electronic energy is called the ground state. 'ny other configuration is an e$cited state. 's an e$ample, the ground state configuration of the sodium atom is 1s//s//p;7s, as deduced from the 'ufbau principle (see below . )he first e$cited state is obtained by promoting a 7s electron to the 7p orbital, to obtain the 1s//s//p;7p configuration, abbreviated as the 7p level. 'toms can move from one configuration to another by absorbing or emitting energy. In a sodium%vapor lamp for e$ample, sodium atoms are e$cited to the 7p level by an electrical discharge, and return to the ground state by emitting yellow light of wavelength :0A nm.

@sually the e$citation of valence electrons (such as 7s for sodium involves energies corresponding to photons of visible or ultraviolet light. )he e$citation of core electrons is possible, but requires much higher energies generally corresponding to $%ray photons. )his would be the case for e$ample to e$cite a /p electron to the 7s level and form the e$cited 1s//s//p:7s/ configuration. )he remainder of this article deals only with the ground%state configuration, often referred to as 9the9 configuration of an atom or molecule.

[edit] History
<iels -ohr was the first to propose (1A/7 that the periodicity in the properties of the elements might be e$plained by the electronic structure of the atom.[:] >is proposals were based on the then current -ohr model of the atom, in which the electron shells were orbits at a fi$ed distance from the nucleus. -ohr.s original configurations would seem strange to a present%day chemist, sulfur was given as /.?.?.; instead of 1s/ /s/ /p; 7s/ 7p? (/.0.; . )he following year, E. (. +toner incorporated +ommerfeld.s third quantum number into the description of electron shells, and correctly predicted the shell structure of sulfur to be /.0.;.[;] >owever neither -ohr.s system nor +toner.s could correctly describe the changes in atomic spectra in a magnetic field (the Beeman effect . -ohr was well aware of this shortcoming (and others , and had written to his friend Colfgang 8auli to as" for his help in saving quantum theory (the system now "nown as 9old quantum theory9 . 8auli reali4ed that the Beeman effect must be due only to the outermost electrons of the atom, and was able to reproduce +toner.s shell structure, but with the correct structure of subshells, by his inclusion of a fourth quantum number and his e$clusion principle (1A/: ,[D] It should be forbidden for more than one electron with the same value of the main quantum number n to have the same value for the other three quantum numbers " [l], # [ml] and m [ms]. )he +chrEdinger equation, published in 1A/;, gave three of the four quantum numbers as a direct consequence of its solution for the hydrogen atom,[/] this solution yields the atomic orbitals which are shown today in te$tboo"s of chemistry (and above . )he e$amination of atomic spectra allowed the electron configurations of atoms to be determined e$perimentally, and led to an empirical rule ("nown as =adelung.s rule (1A7; ,[0] see below for the order in which atomic orbitals are filled with electrons.

[edit] Aufbau principle and Madelung rule

)he 'ufbau principle (from the Ferman Aufbau, 9building up, construction9 was an important part of -ohr.s original concept of electron configuration. It may be stated as,[A]

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 higher energy orbitals.

)he appro$imate order of filling of atomic orbitals, following the arrows. )he principle wor"s very well (for the ground states of the atoms for the first 10 elements, then decreasingly well for the following 166 elements. )he modern form of the 'ufbau principle describes an order of orbital energies given by =adelung.s rule (or *lech"ows"i.s rule . )his rule was first stated by (harles Ganet in 1A/A, rediscovered by Erwin =adelung in 1A7;,[0]and later given a theoretical #ustification by H.=. *lech"ows"i[16] 1. Irbitals are filled in the order of increasing n2lJ /. Chere two orbitals have the same value of n2l, they are filled in order of increasing n. )his gives the following order for filling the orbitals, 1s, /s, /p, 7s, 7p, ?s, 7d, ?p, :s, ?d, :p, ;s, ?f, :d, ;p, Ds, :f, ;d, and Dp )he 'ufbau 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.

[edit] The periodic table

)he form of the periodic table is closely related to the electron configuration of the atoms of the elements. &or e$ample, all the elements of group / have an electron configuration of [E] ns/ (where [E] is an inert gas configuration , and have notable similarities in their chemical properties. )he outermost electron shell is often referred to as the 9valence shell9 and (to a first appro$imation determines the chemical properties. It should be remembered that the similarities in the chemical properties were remar"ed more than a century before the idea of electron configuration,[11] It is not clear how far =adelung.s rule explains (rather than simply describes the periodic table,[1/] although some properties (such as the common 2/ o$idation state in the first row of the transition metals would obviously be different with a different order of orbital filling.

[edit] Shortcomings of the Aufbau principle

)he 'ufbau principle rests on a fundamental postulate that the order of orbital energies is fi$ed, both for a given element and between different elements, neither of these is true (although they are appro$imately true enough for the principle to be useful . It considers atomic orbitals as 9bo$es9 of fi$ed energy into which can be placed two electrons and no more. >owever the energy of an electron 9in9 an atomic orbital depends on the energies of all the other electrons of the atom (or ion, or molecule, etc. . )here are no 9one% electron solutions9 for systems of more than one electron, only a set of many%electron solutions which cannot be calculated e$actly[17] (although there are mathematical appro$imations available, such the >artreeK&oc" method . )he fact that the 'ufbau principle is based on an appro$imation can be seen from the fact that there is an almost%fi$ed filling order at all, that, within a given shell, the s%orbital is always filled before the p%orbitals. In a hydrogen%li"e atom, which only has one electron, the s%orbital and the p%orbitals of the same shell have e$actly the same energy, to a very good appro$imation in the absence of e$ternal electromagnetic fields. (>owever, 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 !amb shift .

[edit] oni!ation of the transition metals

)he naive application of the 'ufbau principle leads to a well%"nown parado$ (or apparent parado$ in the basic chemistry of the transition metals. 8otassium and calcium appear in the periodic table before the transition metals, and have electron configurations ['r] ?s1 and ['r] ?s/ respectively, i.e. the ?s%orbital is filled before the 7d%orbital. )his is in line with =adelung.s rule, as the ?s%orbital has n2l 5 ? (n 5 ?, l 5 6 while the 7d%orbital has n2l 5 : (n 5 7, l 5 / . >owever, chromium and copper have electron configurations ['r] 7d: ?s1 and ['r] 7d16 ?s1 respectively, i.e. one electron has passed from the ?s%orbital to a 7d%orbital to generate a half%filled or filled subshell. In this case, the usual e$planation is that 9half%filled or completely%filled subshells are particularly stable arrangements of electrons9. )he apparent parado$ arises when electrons are removed from the transition metal atoms to form ions. )he first electrons to be ioni4ed come not from the 7d%orbital, as one would e$pect if it were 9higher in energy9, but from the ?s%orbital. )he same is true when chemical compounds are formed. (hromium he$acarbonyl can be described as a chromium atom (not ion, it is in the o$idation state 6 surrounded by si$ carbon mono$ide ligands, it is diamagnetic, and the electron configuration of the central chromium atom is described as 7d;, i.e. the electron which was in the ?s%orbital in the free atom has passed into a 7d%orbital on forming the compound. )his interchange of electrons between ?s and 7d is universal among the first series of the transition metals.[1?] )he phenomenon is only parado$ical if it is assumed that the energies of atomic orbitals are fi$ed and unaffected by the presence of electrons in other orbitals. If that were the case, the 7d%orbital would have the same energy as the 7p%orbital, as it does in hydrogen, yet it clearly doesn.t. )here is no special reason why the &e/2 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. Chen care is ta"en to compare 9li"e with li"e9, the parado$ disappears.[1:]

[edit] "ther exceptions to Madelung#s rule

)here are several more e$ceptions to =adelung.s rule among the heavier elements, and it is more and more difficult to resort to simple e$planations such as the stability of half% filled subshells. It is possible to predict most of the e$ceptions by >artreeK&oc" calculations,[1;] which are an appro$imate method for ta"ing account of the effect of the other electrons on orbital energies. &or the heavier elements, it is also necessary to ta"e account of the effects of +pecial Lelativity 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[1D] tend to decrease the energy of the s%orbitals in relation to the other atomic orbitals.[10] Electron shells filled in violation of =adelung.s rule (red $eriod % Element Electron ( )onfigurati Element on !anthanum (erium $eriod & Electron ( )onfigurati Element on : [Me] ;s/ :d1 D : [Me] ;s/ ?f1 0 :d1 'ctinium )horium $eriod ' Electron ( )onfigurati on 0A [Ln] Ds/ ;d1 A6 [Ln] Ds/ ;d/

8raseodymi : [Me] ;s/ ?f7 um A <eodymium 8romethium +amarium Europium Fadolinium )erbium ; [Me] ;s/ ?f? 6 ; [Me] ;s/ ?f: 1 ; [Me] ;s/ ?f; / ; [Me] ;s/ ?fD 7 ; [Me] ;s/ ?fD ? :d1 ; [Me] ;s/ ?fA :

8rotactiniu [Ln] Ds/ :f/ A1 m ;d1 @ranium A/ [Ln] Ds/ :f7 ;d1 [Ln] Ds/ :f? ;d1

<eptunium A7 8lutonium

A? [Ln] Ds/ :f;

'mericium A: [Ln] Ds/ :fD (urium -er"elium A; [Ln] Ds/ :fD ;d1

AD [Ln] Ds/ :fA


7 [*r] :s/ ?d1 A


D [Me] ;s/ ?f1? 16 [Ln] Ds/ :f1? !awrencium 1 1 :d 7 Dp1

Birconium <iobium

? [*r] :s/ ?d/ 6 ? [*r] :s1 ?d? 1

>afnium )antalium )ungsten Lhenium Ismium Iridium 8latinum

D [Me] ;s/ ?f1? Lutherfordi 16 !un"nown# / :d/ um ? D [Me] ;s/ ?f1? 7 :d7 D [Me] ;s/ ?f1? ? :d? D [Me] ;s/ ?f1? : :d: D [Me] ;s/ ?f1? ; :d; D [Me] ;s/ ?f1? D :dD D [Me] ;s1 ?f1? 0 :dA D [Me] ;s1 ?f1? A :d16 0 [Me] ;s/ ?f1? 6 :d16 0 [Me] ;s/ ?f1? 1 :d16 ;p1

=olybdenu ? [*r] :s1 ?d: m / )echnetiu ? [*r] :s/ ?d: m 7 Luthenium Lhodium 8alladium +ilver (admium Indium ? [*r] :s1 ?dD ? ? [*r] :s1 ?d0 : ? [*r] ?d16 ;

? [*r] :s1 ?d16 Fold D ? [*r] :s/ ?d16 =ercury 0 ? [*r] :s/ ?d16 )hallium A :p1

-y the =adelung rule, 167 !awrencium would be an e$pected O[Ln] Ds/ :f1? ;d1. )he electron%shell configuration of heavier elements is not yet "nown.

[edit] Electron configuration in molecules

In molecules, the situation becomes more comple$, as each molecule has a different orbital structure. )he molecular orbitals are labelled according to their symmetry,[1A] rather than the atomic orbital labels used for atoms and monoatomic ions, hence, the electron configuration of the dio$ygen molecule, I/, is 1Pg/ 1Pu/ /Pg/ /Pu/ 1Qu? 7Pg/ 1Qg/.[1] )he term 1Qg/ represents the two electrons in the two degenerate QO%orbitals (antibonding . &rom >und.s rules, these electrons have parallel spins in the ground state, and so dio$ygen has a net magnetic moment (it is paramagnetic . )he e$planation of the paramagnetism of dio$ygen was a ma#or success for molecular orbital theory.

[edit] Electron configuration in solids

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

[edit] Applications

)he most widespread application of electron configurations is in the rationali4ation 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 e$pected to form. )his approach is ta"en further in computational chemistry, which typically attempts to ma"e quantitative estimates of chemical properties. &or many years, most such calculations relied upon the 9linear combination of atomic orbitals9 (!('I appro$imation, using an ever larger and more comple$ basis set of atomic orbitals as the starting point. )he last step in such a calculation is the assignment of electrons among the molecular orbitals according to the 'ufbau principle. <ot all methods in calculational chemistry rely on electron configuration, density functional theory (R&) is an important e$ample of a method which discards the model. ' fundamental application of electron configurations is in the interpretation of atomic spectra. In this case, it is necessary to convert the electron configuration into one or more term symbols, which describe the different energy levels available to an atom. )erm symbols can be calculated for any electron configuration, not #ust the ground%state configuration listed in tables, although not all the energy levels are observed in practice. It is through the analysis of atomic spectra that the ground%state electron configurations of the elements were e$perimentally determined.