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Encyclopedia > Term symbol

In quantum mechanics, the term symbol is an abbreviated description of the angular momentum quantum numbers in a multi-electron atom. It is related with the energy level of a given electron configuration. LS coupling is assumed. The ground state term symbol is predicted by the Hund's rules. Fig. ... The Principal quantum number (usually written n) is the first quantum number of an atomic orbital. ... Properties The electron is a fundamental subatomic particle which carries a negative electric charge. ... Properties For alternative meanings see atom (disambiguation). ... Electron atomic and molecular orbitals In atomic physics, the electron configuration is the arrangement of electrons in an atom, molecule or other body. ... In quantum mechanics, the orbital and spin angular momentum of bodies can interact in angular momentum coupling. ... In atomic physics, Hunds rules, discovered by Friedrich Hund, determine which is the term symbol that corresponds to the ground state of a multi-electron atom. ...


The term symbol has the form

{}^{2S+1}!L_{J}

where

and J is the total angular momentum quantum number.

When used to describe electron states in an atom, the term symbol usually follows the electron configuration, e.g., in the carbon case, the ground state is 1s22s22p2 3P0. In physics, spin is an intrinsic angular momentum associated with microscopic particles. ... The Azimuthal quantum number (or orbital angular momentum quantum number) l is a quantum number for an atomic orbital which determines its orbital angular momentum. ... Before the atom electron states were known, spectroscopists saw distintive series in atom spectra, and so they asigned letters to characteristic spectra. ... The total angular quantum momentum numbers parameterize the total angular momentum of a given electron, by combining its orbital angular momentum and its intrinsic angular momentum (i. ... Electron atomic and molecular orbitals In atomic physics, the electron configuration is the arrangement of electrons in an atom, molecule or other body. ... General Name, Symbol, Number carbon, C, 6 Chemical series nonmetals Group, Period, Block 14, 2, p Appearance black (graphite) colorless (diamond) Atomic mass 12. ...


The term symbol is also used to describe compound systems such as mesons or atomic nuclei, or even molecules (see molecular term symbol). In that last case, greek letters are used to designate the (molecular) orbital angular momenta. In particle physics, a meson is a strongly interacting boson, that is, it is a hadron with integral spin. ... In molecular physics, the molecular term symbol is a shorthand expression of the group representation and angular momenta that characterize the state of a molecule, i. ...


For a given electron configuration

  • The combination of an S value and a L value is called a term, and has a statistical weight (i.e., number of possible microstates) of (2S+1)(2L+1);
  • A combination of S, L and J is called a level. A given level has a statistical weight of (2J+1), which is the number of possible microstates associated with this level in the corresponding term;
  • A combination of L, S, J and MJ determines a single state.

As an example, for S = 1, L = 2, and J = 3, there are (2×1+1)(2×2+1) = 15 different microstates corresponding to the 3D term, of which (2×3+1) = 7 belong to the 3D3 level. The sum of (2J+1) for all levels in the same term equals (2S+1)(2L+1). In this case, J can be 1, 2, or 3, so 3 + 5 + 7 = 15.

Contents


Term symbol parity

The parity of a tem symbol is calculated as

P=(-1)^{sum_i l_i},!,

where li is the orbital quantum number for each electron. In fact, only electrons in odd orbitals contribute to the total parity: an odd number of electrons in odd orbitals (those with an odd l such as in p, f,...) will make an odd term symbol, while an even number of electrons in odd orbitals will make an even term symbol, irrespective of the number of electrons in even orbitals.


When it is odd, the parity of the term symbol is indicated by a superscript letter "o", otherwise it is omitted:

{}^2!mathrm P_{1/2}^o has odd parity, but {}^3!mathrm P_0 has even parity.

Alternatively, parity may be indicated with a subscript letter "g" or "u", standing for gerade (even in German) or ungerade (odd):

{}^2!mathrm P_{1/2,u} for odd parity and {}^3!mathrm P_{0,g} for even.

Ground state term symbol

It is relatively easy to calculate the term symbol for the ground state of an atom. It corresponds with a state with maximal S and L.

  1. Start with the most stable electron configuration. Full shells and subshells do not contribute to the overall angular momentum, so they are discarded.
    • If all shells and subshells are full then the term symbol is {}^1!S_0.
  2. Distribute the electrons in the available orbitals, following Pauli exclusion principle. First, we fill the orbitals with highest ml value with one electron each, and assign a maximal ms to them (i.e. +1/2). Once all orbitals in a subshell have one electron, add a second one (following the same order), assigning ms = −1/2 to them.
  3. The overall S is calculated by adding the ms values for each electron. That is the same as multiplying ½ times the number of unpaired electrons. The overall L is calculated by adding the ml values for each electron (so if there are two electrons in the same orbital, then we add twice that orbital's ml).
  4. Calculate J as:
    • if less than half of the subshell is occupied, take the minimum value: J = | LS |
    • if more than half-filled, take the maximum valueJ = L + S.
    • if the subshell is half-filled, then L will be 0, so J = S.


As an example, in the fluorine case the electronic configuration is: 1s22s22p5. Electron atomic and molecular orbitals In atomic physics, the electron configuration is the arrangement of electrons in an atom, molecule or other body. ... In physics, angular momentum is analogous to (linear) momentum except that it applies to rotating objects. ... The term orbital has several meanings: In physics and chemistry it is used to describe an atomic electron configuration, see also molecular orbital and atomic orbital. ... The Pauli exclusion principle is a quantum mechanical principle formulated by Wolfgang Pauli in 1925, which states that no two identical fermions may occupy the same quantum state. ... By virtue of its charge and spin motion, an electron develops a magnetic field. ... In physics, spin is an intrinsic angular momentum associated with microscopic particles. ... The total angular quantum momentum numbers parameterize the total angular momentum of a given electron, by combining its orbital angular momentum and its intrinsic angular momentum (i. ... General Name, Symbol, Number fluorine, F, 9 Chemical series halogens Group, Period, Block 17, 2, p Appearance pale greenish-yellow gas Atomic mass 18. ...


1. Discart the full subshells and keep the 2p5 part. So we have five electrons to place in subshell p (l = 1).


2. There are three orbitals (ml = 1, 0, −1) that can hold up to 2(2l+1) = 6 electrons. The first three electrons can take ms = 1/2 (↑) but the Pauli exclusion principle force the next two to have ms = −1/2 (↓) because they go to already ocupied orbitals

  ml
+1 0 −1
ms: ↑↓ ↑↓

3. S = 1/2 + 1/2 + 1/2 − 1/2 − 1/2 = 1/2; and L = 1 + 0 − 1 + 1 + 0 = 1, which is "P" in spectroscopic notation;


4. As fluorine 2p subshell is more than half filled, J = L + S = 3/2. Its ground state term symbol is then {}^{2S+1}!L_J = {}^2!mathrm P_{3/2}.


Term symbols for an electron configuration

To calculate all possible term symbols for a given electron configuration the process is a bit longer. Electron atomic and molecular orbitals In atomic physics, the electron configuration is the arrangement of electrons in an atom, molecule or other body. ...

  • First, calculate the total number of possible microstates N for a given electron configuration. As before, we discard the filled (sub)shells, and keep only the partially-filled ones. For a given orbital quantum number l the total number of electrons that can be fitted is t = 2(2l+1). If there are e electrons in a given subshell, the number of possible microstates is
N= {t choose e} = {t! over {e!,(t-e)!}}.
As an example, lets take the carbon electron structure: 1s22s22p2. After removing full subshells, there are 2 electrons in a p-level (l = 1), so we have
N = {6! over {2!,4!}}=15
different microstates.
  • Second, draw all possible microstates. Calculate ML and MS for each microstate, with M=sum_{i=1}^e m_i where mi is either ml or ms for the i-th electron, and M represents the resulting ML or MS respectively:
  ml  
  +1 0 −1 ML MS
all up 1 1
0 1
−1 1
all down 1 −1
0 −1
−1 −1
one up

one down General Name, Symbol, Number carbon, C, 6 Chemical series nonmetals Group, Period, Block 14, 2, p Appearance black (graphite) colorless (diamond) Atomic mass 12. ...

↑↓ 2 0
1 0
0 0
1 0
↑↓ 0 0
−1 0
0 0
−1 0
↑↓ −2 0
  • Third, count the number of microstates for each MLMS possible combination
  MS
  +1 0 −1
ML +2 1
+1 1 2 1
0 1 3 1
−1 1 2 1
−2 1
  • Forth, extract smaller tables representing each possible term. Each table will be (2L+1)(2S+1), and will contain "1"s as entries. The first table extracted corresponds to ML ranging from −2 to +2 (so L = 2), with a single value for MS (implying S = 0). This corresponds to a 1D term. The remaining table is 3×3. Then we extract a second table, removing the entries for ML and MS both ranging from −1 to +1 (and so S = L = 1, a 3P term). The remaining table is a 1×1 table, with L = S = 0, i.e., a 1S term.

S=0, L=2, J=2

1D2

  Ms
  0
Ml +2 1
+1 1
0 1
−1 1
−2 1

S=1, L=1, J=2,1,0

3P2, 3P1, 3P0

  Ms
  +1 0 −1
Ml +1 1 1 1
0 1 1 1
−1 1 1 1

S=0, L=0, J=0

1S0

  Ms
  0
Ml 0 1
  • Fifth, applying Hund's rules, order the states by increasing order of energy:
3P0 < 3P1 < 3P2 < 1D2 < 1S0

See also


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