CY 1051 : Introduction to spectroscopic methods

Semester : Jan May 2016

Teacher : G. Ranga Rao

Atomic spectroscopy and term symbols: quantum numbers for multi-electron species

Russell-Saunders (R-S) coupling scheme is an important coupling scheme to determine the terms and to
assign the term symbols to the terms to the valence electrons of free atoms. The atomic term symbols
provide the information about the energy of atomic valence electrons, total spin, total orbital angular
momentum, total angular momentum, spectral and magnetic properties of atom.

There are three types of interactions between the electrons : spin-spin coupling, orbit-orbit coupling and
spin-orbit coupling. Generally, orbit-orbit coupling > spin-spin coupling > spin-orbit coupling. There are
two principle coupling schemes, (i) Russell-Saunders coupling and (ii) j - j coupling adopted for arising or
splitting of state in a free atom. The Russell-Saunders scheme gives a good approximation for the first
row transition series elements where spin-orbit (j-j) coupling scheme can generally be ignored, however
for elements with atomic number greater than thirty, spin-orbit coupling becomes more significant due
to higher nuclear charge and the j-j coupling scheme is used.

In multi-electron systems, electrons interact with each other due to:

(i) electrostatic repusion between electrons
(ii) interaction or coupling of magnetic fields produced by their spins
(iii) couping of the fields produced by the orbital motion of the electrons (orbital angular momentum)
When several electrons occupy the sub-shell the energy states depend on the result of
the orbital quantum numbers of each of the electrons.
This resultant of all the l values is denoted by new quantum number L and so on.

These interactions (coupling) produced by the electrons orbital and spin angular momentum give rise to
a series of energy levels or states which are characterized by energy, orbital angular momentum, spin
angular momentum and total angular momentum and expressed by proper term symbols, and defined
by new quantum numbers L, ML, MS and S. For multi electron systems these are obtained summing
vectorially the quantum numbers for the individual electrons. The terms have orbital degeneracy (2L+1)
and spin degeneracy (2S+1). We shall discuss L-S coupling scheme here.

Information Term symbols provide:

(i) Total orbital angular momentum, L (due to coulombic interactions)
(ii) Multiplicity of the term is (2S+1), (2S+1)=1,2,3,4,(corresponding to S = 0, , 1, 3/2, ) are
called singlets, doublets, triplets, quartets, (due to exchange interactions)
(iii) Total angular momentum, J (due to spin-orbit interactions)

2 S 1
Term symbol : LJ

G. Ranga Rao (CY 1051) Jan May 2016

L is the resultant orbital quantum number, S is the resultant spin quantum number (remember S is also
used for Term for which L=0), J is the total angular momentum quantum number.

For any system containing more than one electron, the energy of an electron in shell of principal
quantum number n depends on the value of l which determines the orbital angular momentum of the
h
electrons: Orbital angular momentum = l( l 1)
2

Likewise the energy of a multi-electron species and its orbital angular momentum is determined by a
resultant orbital quantum number, L, which can be obtained directly from the values of l for the
individual electrons. The orbital angular momentum has a magnitude and (2l+1) special orientations (the
ml values). The component of orbital angular momentum along z-axis is given by ml for any electron and
the algebraic summation of ml values for individual electrons gives the resultant orbital magnetic
quantum number ML. Just as ml may have the (1l+1) values of l, (l-1),0-(l-1),-l, so ML can have
(2L+1) values of L, i.e. L, (L-1),0-(L-1),-L. If we can find all possible values of ML for a multi-electron
system, we can then obtain the value of L. Energy states for L= 0, 1, 2, 3, 4, .are known as S, P, D, F,
G, terms, respectively.
h
Orbital angular momentum for multi-electron species = L( L 1)
2
h
Spin angular momentum for multi-electron species = S ( S 1)
2

MS is obtained by algebraic summation of the ml values for individual electrons. One electron with s=1/2
has S=1/2 with MS = +1/2 or -1/2; MS for the multi-electron system is analogous to ms for the one-
1 1
electron species. Two electrons leads to S=0 i.e. ms and giving MS =0 , or S=1
2 2
1 1 1 1 1 1
i.e. ms and , or and or and giving MS =1,0 or 1 .
2 2 2 2 2 2
In general for any value of S, there are (2S+1) values of MS : S, (S-1), .0-(S-1),-S.
(2S+1)=1,2,3,4,(corresponding to S = 0, , 1, 3/2, ) are called singlets, doublets, triplets, quartets,
h
The total angular momentum for a multilectron system = J ( J 1)
2

J can be obtained vectorially from L and S, i.e. algebraically from ML and MS.
J can take values, ( L S ), ( L S 1) , ..... L S . J must be positive or zero. There are
(2S+1) possible values of J for S < L, and (2L+1) possible values for L < S.
This method of obtaining J from L and S is called L-S coupling.

G. Ranga Rao (CY 1051) Jan May 2016

Atomic term symbols for electronic energy levels of polyelectronic atoms:
2 S 1
If we know (2S+1), L, and J for an energy state, we can write Term symbol : L J . For example
electronic ground state of carbon is 3 P0 (read as "triplet P zero") which means L = 1, S=1, and J =0.
Different J values, J, 0,+J , denote different levels within the term.
Exampe : H (1s1 )
l 0, so L = l1 l2 l3 .... 0 S term
1
Total spin quantum number S and (2S 1) 2 (doublet term)
2
1
J Term symbol for H atom in 1s1 state is 2S1/2
2

Example : He (1s 2 )
Both electrons have l 0,
L = l1 l2 , l1 l2 , 1, l1 l2 2,.... l1 l2 , so L = 0
Maximum L corresponds to l1 l2 and minimum L corresponds to l1 l2 .
1 1
Both electrons with n 1 and l 0, must have ms and
2 2
Total spin quantum number S 0 and (2S 1) 1 (a singlet term)
J 0 Term symbol for He atom in 1s1 state is 1S0 .

Example : 2p 2 atomic configuration

This can have 15 possible electronic arrangements i.e. 15 microstates (see figure).
We have L values 2,1,0 corrsponding to D, P, and S states with different energies.
S values 1 or 0 corresponding multiplicities of 1 and 3.
For S 1, 2 S 1 3 ...called a triplet state
For S 0, 2 S 1 1 ...called a singlet state
Possible states : 3 D, 3 P, 3 S , 1D, 1P, 1S .
Pauli exclusion principle allows only 3 P, 1D, 1S states.

Total angualr momentum: J

Permitted values of J : J = L S , L S 1, L S 2,.... L S
L 1, S 1, J 2, 1, 0 Term symbol : 3 P2 , 3 P1, 3 P0
L 2, S 0, J 2 Term symbol : 1D2
L 0, S 0, J 0 Term symbol : 1S0

G. Ranga Rao (CY 1051) Jan May 2016

15 ways to place two electrons in the same p-shell and therefore
there are 15 states associated with 1s22s22p2.

G. Ranga Rao (CY 1051) Jan May 2016

Assigning energies to terms (Hunds Rules)

Ground state will have the largest spin multiplicity (S) i.e. 3P is lower in energy than 1P
Two states with the same spin multiplicity can be distinguished by L values.
The state with the largest L is of lowest energy, i.e. 1D < 1S
After checking the above : if the subshell is less than half-full, the lowest J corresponds to the
lowest energy (most stable). If the subshell is greater than half-full, the
highest J corresponds to the lowest energy (most stable).

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G. Ranga Rao (CY 1051) Jan May 2016