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Review Sheet On Determining Term Symbols
Review Sheet On Determining Term Symbols
Term symbols for electronic configurations are useful not only to the
spectroscopist but also to the inorganic chemist interested in understanding electronic and
magnetic properties of molecules. We will concentrate on the method of Douglas and
McDaniel (p. 26ff); however, you may find other treatments equal or superior to the D &
M method.
Term symbols are a shorthand method used to describe the energy, angular
momentum, and spin multiplicity of an atom in any particular state. The general form is
given as aTj where T is a capital letter corresponding to the value of L (the angular
momentum quantum number) and may be assigned as S, P, D, F, G, for |L| = 0, 1, 2, 3,
4, respectively. The superscript a is called the spin multiplicity and can be
evaluated as a = 2S +1 where S is the spin quantum number. The subscript j is the
numerical value of J, a new quantum number defined as: J = l +S, which corresponds to
the total orbital and spin angular momentum of the system. The term symbol 3P is read
as triplet Pee state and indicates that there are two unpaired electrons in a state with
maximum orbital angular momentum, L=1.
The number of microstates (N) of a system corresponds to the total number of
distinct arrangements for e number of electrons to be placed in n number of possible
orbital positions.
N = # of microstates = n!/(e!(n-e)!)
For a set of p orbitals n = 6 since there are 2 positions in each orbital. Therefore, p2 (e =
2 and n = 6) so,
N = 6!/(2!(6-2)!) = (6*5*4*3*2*1)/((2*1) * (4*3*2*1)) = 15
We can introduce the idea of a hole formalism which states that for many
electronic properties one may consider systems with e or (n-e), the number of unoccupied
sites or holes, to be equivalent. Thus,
P4 (e = 4 and n = 6)
N = 6!/(4!(6-4)!) = 15
so P4 (2 holes) and P2 (4 holes) give equivalent values of N. The same is true for all p, d,
f, systems such as d1/d9 or f2/f12.
If one should consider an atom with multiple unoccupied orbitals, the total
number of microstates will equal the product of the microstates for the individual orbitals.
(N = N*a; a = 1 to i where a = orbital index). For an s1p2 configuration N = 2 (from S1)
* 15 (from p2) = 30.
We can define component ML in two ways. First,
M L = m1 + m2 + m3 +
where ml corresponds to the l angular momentum quantum number for each electron
in a given orientation. Second,
ML = L, L-1, , 0, , -L
where L is the atomic orbital angular momentum. Thus, ML has 2L + 1 values.
Similar definitions for MS, representing the spin of the system may be made with
allowable values of MS = 2S+1
The total angular momentum quantum number, J, is given as J = L+S, L+S 1,
, |L-S|. It is the absolute magnitude of J that determines the total angular momentum.
Determination of Spectroscopic Terms
1.
2.
3.
4.
5.
ML
MS
3
2
1
0
1
0
-1
-1
-2
-3
+1
+1
+1
+1
+1
+1
+1
+1
+1
+1
ml
=
+2
+1
ms=
+1/2
0
-1
-2
Ms
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
ml
=
+2
+1
ms=
-1/2
0
-1
-2
ML
MS
4
3
2
1
0
3
2
1
0
-1
2
1
0
-1
-2
1
0
-1
-2
-3
0
-1
-2
-3
-4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
ml
=
+2
+1
ms=
+1/2
0
-1
-2
ml
=
+2
+1
ms=
-1/2
0
-1
-2
ML
+4
+3
+2
+1
0
-1
-2
-3
-4
1
1
2
2
2
1
1
+1
1
2
3
4
5
4
3
2
1
0
MS
1
1
2
2
2
1
1
-1
The sum of the values in this chart must total 45, the total number of microstates.
STEP 5. Resolve Microstates
We can immediately see that there is a microstate which must correspond to ML =
-4 and MS = 0. This must be a G state since L = 4 and it must be an orbital singlet since
MS = 0. Therefore, the first term is 1G (We will assign J values later.). A 1G
representation corresponds to a 9 x 1 matrix (ML x MS) since L can range from +4
through 4 (9 elements) and S can only equal 0 (1 element). Removing 9 microstates
from Table 1 yields Table 2.
Table 2.
ML
+3
+2
+1
0
-1
-2
-3
1
1
2
2
2
1
1
+1
1
2
3
4
3
2
1
0
MS
1
1
2
2
2
1
1
-1
Now go to the upper left corner (italicized and red) element. The ML and MS value for
this element yield the next microstate representation. ML=3 therefore F, MS =1 therefore
triplet, so the element is 3F.
3
F is a 7 x 3 matrix = 21 microstates that are removed to give Table 3.
Table 3.
ML
+2
+1
0
-1
-2
1
1
1
+1
1
2
3
2
1
0
MS
1
1
1
-1
+1
0
-1
1
1
1
+1
1
2
1
0
MS
1
1
1
-1
1
0
MS
Assigning J Values
J = L + S: number of microstates = 2J + 1
G ! 1G4
(L = 4, S = 0)
9 microstates
S ! 1S0
(L = 0, S = 0)
1 microstate
1
1
D ! D2
(L = 2, S = 0)
5 microstates
3
F ! 3F4
(L = 3, S = 1)
9 microstates
3
3
P ! P2
(L = 1, S = 1)
5 microstates
Notice that the total number of microstates does not equal 45 at this point! All of the
microstates associated with 1G, 1S, and 1D are accounted for, while 12 3F microstates and
4 3P microstates are missing. This is because we have only calculated the state of
maximum multiplicity! Both the 3F and 3P states can be factored. We do this by lowering
the J value by one until all microstates have been accounted for. Thus,
For
1
1
F4 (9 microstates)
F3 (7 microstates)
3
F2 (5 microstates)
3
21 microstates
P2 (5 microstates)
P1 (3 microstates)
3
P0 (1 microstate)
3
9 microstates
S
1
1
D
G
S0
D2
G4
G
3
s2p6d2
1
3
P2
P1
3
P0
3
F4
F3
3
F2
3
Actual