Find all the terms for the d3 configuration:
To describe each microstate, use the notation: (ml±, ml±, ml±) where + means ms =+ ½ and - means ms =- ½
maximum possible L = 5 (2+, 2-, 1+), so ML = 5, 4, 3, 2, 1, 0, -1, -2, -3, -4, -5
maximum possible S = 3/2 (2+, 1+, 0+), so MS = 3/2, 1/2, -1/2, -3/2
Build and fill the bookkeeping matrix:
| ML\MS |
|
|
|
|
| 5 |
|
|
||
| 4 |
|
|
||
| 3 |
|
(2+, 1+, 0-) (2+, 2-, -1+) |
(2-, 1-, 0+) (2-, 2+, -1-) |
|
| 2 |
|
(2+, 1+, -1-) (2+, 0+, 0-) (1+, 1-, 0+) (2+, 2-, -2+) |
(2-, 1-, -1+) (2-, 0-, 0+) (1-, 1+, 0-) (2-, 2+, -2-) |
|
| 1 |
|
(2+, 1+, -2-) (2-, 0+, -1+) (2+, 0-, -1+) (2+, 0+, -1-) (1+, 0+, 0-) (1+, 1-, -1+) |
(2-, 1-, -2+) (2+, 0-, -1-) (2-, 0+, -1-) (2-, 0-, -1+) (1-, 0-, 0+) (1-, 1+, -1-) |
|
| 0 |
|
(2+,0+,-2-) (1-,0+,-1+) (1+,0-,-1+) (1+,0+,-1-) (2+, -1+, -1-) (1+, 1-, -2+) |
(2-,0-,-2+) (1+,0-,-1-) (1-,0+,-1-) (1-,0-,-1+) (2-, -1-, -1+) (1-, 1+, -2-) |
|
| -1 |
|
(-2+, -1+, 2-) (-2-, 0+, 1+) (-2+, 0-, 1+) (-2+, 0+, 1-) (-1+, 0+, 0-) (-1+, -1-, 1+) |
(-2-, -1-, 2+) (-2+, 0-, 1-) (-2-, 0+, 1-) (-2-, 0-, 1+) (-1-, 0-, 0+) (-1-, -1+, 1-) |
|
| -2 |
|
(-2+, -1+, 1-) (-2+, 0+, 0-) (-1+, -1-, 0+) (-2+, -2-,2+) |
(-2-, -1-, 1+) (-2-, 0-, 0+) (-1-, -1+, 0-) (-2-, -2+,2-) |
|
| -3 |
|
(-2+, -1+, 0-) (-2+, -2-,1+) |
(-2-, -1-, 0+) (-2-, -2+,1-) |
|
| -4 |
|
|
||
| -5 |
|
|
The total number of microstates =
(Nl
=2[2(2)+1] =10, x =3), which matches the number in the matrix.
Now find terms:
First term is ML = 3 , MS =3/2 giving 4F
The degeneracy of the 4F state is [2(3)+1]×[2(3/2)+1] = 28, so 28 microstates must be eliminated.
red denoted states eliminated by 4F:
| ML\MS |
|
|
|
|
| 5 |
|
|
||
| 4 |
|
|
||
| 3 |
|
(2+, 1+, 0-) (2+, 2-, -1+) |
(2-, 1-, 0+) (2-, 2+, -1-) |
|
| 2 |
|
(2+, 1+, -1-) (2+, 0+, 0-) (1+, 1-, 0+) (2+, 2-, -2+) |
(2-, 1-, -1+) (2-, 0-, 0+) (1-, 1+, 0-) (2-, 2+, -2-) |
|
| 1 |
|
(2+, 1+, -2-) (2-, 0+, -1+) (2+, 0-, -1+) (2+, 0+, -1-) (1+, 0+, 0-) (1+, 1-, -1+) |
(2-, 1-, -2+) (2+, 0-, -1-) (2-, 0+, -1-) (2-, 0-, -1+) (1-, 0-, 0+) (1-, 1+, -1-) |
|
| 0 |
|
(2+,0+,-2-) (1-,0+,-1+) (1+,0-,-1+) (1+,0+,-1-) (2+, -1+, -1-) (1+, 1-, -2+) |
(2-,0-,-2+) (1+,0-,-1-) (1-,0+,-1-) (1-,0-,-1+) (2-, -1-, -1+) (1-, 1+, -2-) |
|
| -1 |
|
(-2+, -1+, 2-) (-2-, 0+, 1+) (-2+, 0-, 1+) (-2+, 0+, 1-) (-1+, 0+, 0-) (-1+, -1-, 1+) |
(-2-, -1-, 2+) (-2+, 0-, 1-) (-2-, 0+, 1-) (-2-, 0-, 1+) (-1-, 0-, 0+) (-1-, -1+, 1-) |
|
| -2 |
|
(-2+, -1+, 1-) (-2+, 0+, 0-) (-1+, -1-, 0+) (-2+, -2-,2+) |
(-2-, -1-, 1+) (-2-, 0-, 0+) (-1-, -1+, 0-) (-2-, -2+,2-) |
|
| -3 |
|
(-2+, -1+, 0-) (-2+, -2-,1+) |
(-2-, -1-, 0+) (-2-, -2+,1-) |
|
| -4 |
|
|
||
| -5 |
|
|
The next state found is ML =1, MS =3/2, which
is 4P, accounting for 12 microstates (green)
| ML\MS |
|
|
|
|
| 5 |
|
|
||
| 4 |
|
|
||
| 3 |
|
(2+, 1+, 0-) (2+, 2-, -1+) |
(2-, 1-, 0+) (2-, 2+, -1-) |
|
| 2 |
|
(2+, 1+, -1-) (2+, 0+, 0-) (1+, 1-, 0+) (2+, 2-, -2+) |
(2-, 1-, -1+) (2-, 0-, 0+) (1-, 1+, 0-) (2-, 2+, -2-) |
|
| 1 |
|
(2+, 1+, -2-) (2-, 0+, -1+) (2+, 0-, -1+) (2+, 0+, -1-) (1+, 0+, 0-) (1+, 1-, -1+) |
(2-, 1-, -2+) (2+, 0-, -1-) (2-, 0+, -1-) (2-, 0-, -1+) (1-, 0-, 0+) (1-, 1+, -1-) |
|
| 0 |
|
(2+,0+,-2-) (1-,0+,-1+) (1+,0-,-1+) (1+,0+,-1-) (2+, -1+, -1-) (1+, 1-, -2+) |
(2-,0-,-2+) (1+,0-,-1-) (1-,0+,-1-) (1-,0-,-1+) (2-, -1-, -1+) (1-, 1+, -2-) |
|
| -1 |
|
(-2+, -1+, 2-) (-2-, 0+, 1+) (-2+, 0-, 1+) (-2+, 0+, 1-) (-1+, 0+, 0-) (-1+, -1-, 1+) |
(-2-, -1-, 2+) (-2+, 0-, 1-) (-2-, 0+, 1-) (-2-, 0-, 1+) (-1-, 0-, 0+) (-1-, -1+, 1-) |
|
| -2 |
|
(-2+, -1+, 1-) (-2+, 0+, 0-) (-1+, -1-, 0+) (-2+, -2-,2+) |
(-2-, -1-, 1+) (-2-, 0-, 0+) (-1-, -1+, 0-) (-2-, -2+,2-) |
|
| -3 |
|
(-2+, -1+, 0-) (-2+, -2-,1+) |
(-2-, -1-, 0+) (-2-, -2+,1-) |
|
| -4 |
|
|
||
| -5 |
|
|
The next state found is ML =5, MS =1/2, which
is 2H, accounting for 22 microstates (blue)
| ML\MS |
|
|
|
|
| 5 |
|
|
||
| 4 |
|
|
||
| 3 |
|
(2+, 1+, 0-) (2+, 2-, -1+) |
(2-, 1-, 0+) (2-, 2+, -1-) |
|
| 2 |
|
(2+, 1+, -1-) (2+, 0+, 0-) (1+, 1-, 0+) (2+, 2-, -2+) |
(2-, 1-, -1+) (2-, 0-, 0+) (1-, 1+, 0-) (2-, 2+, -2-) |
|
| 1 |
|
(2+, 1+, -2-) (2-, 0+, -1+) (2+, 0-, -1+) (2+, 0+, -1-) (1+, 0+, 0-) (1+, 1-, -1+) |
(2-, 1-, -2+) (2+, 0-, -1-) (2-, 0+, -1-) (2-, 0-, -1+) (1-, 0-, 0+) (1-, 1+, -1-) |
|
| 0 |
|
(2+,0+,-2-) (1-,0+,-1+) (1+,0-,-1+) (1+,0+,-1-) (2+, -1+, -1-) (1+, 1-, -2+) |
(2-,0-,-2+) (1+,0-,-1-) (1-,0+,-1-) (1-,0-,-1+) (2-, -1-, -1+) (1-, 1+, -2-) |
|
| -1 |
|
(-2+, -1+, 2-) (-2-, 0+, 1+) (-2+, 0-, 1+) (-2+, 0+, 1-) (-1+, 0+, 0-) (-1+, -1-, 1+) |
(-2-, -1-, 2+) (-2+, 0-, 1-) (-2-, 0+, 1-) (-2-, 0-, 1+) (-1-, 0-, 0+) (-1-, -1+, 1-) |
|
| -2 |
|
(-2+, -1+, 1-) (-2+, 0+, 0-) (-1+, -1-, 0+) (-2+, -2-,2+) |
(-2-, -1-, 1+) (-2-, 0-, 0+) (-1-, -1+, 0-) (-2-, -2+,2-) |
|
| -3 |
|
(-2+, -1+, 0-) (-2+, -2-,1+) |
(-2-, -1-, 0+) (-2-, -2+,1-) |
|
| -4 |
|
|
||
| -5 |
|
|
The next state found is ML =4, MS =1/2, which
is 2G, accounting for 18 microstates (pink)
| ML\MS |
|
|
|
|
| 5 |
|
|
||
| 4 |
|
|
||
| 3 |
|
(2+, 1+, 0-) (2+, 2-, -1+) |
(2-, 1-, 0+) (2-, 2+, -1-) |
|
| 2 |
|
(2+, 1+, -1-) (2+, 0+, 0-) (1+, 1-, 0+) (2+, 2-, -2+) |
(2-, 1-, -1+) (2-, 0-, 0+) (1-, 1+, 0-) (2-, 2+, -2-) |
|
| 1 |
|
(2+, 1+, -2-)(2-, 0+, -1+) (2+, 0-, -1+) (2+, 0+, -1-) (1+, 0+, 0-) (1+, 1-, -1+) |
(2-, 1-, -2+)(2+, 0-, -1-) (2-, 0+, -1-) (2-, 0-, -1+) (1-, 0-, 0+) (1-, 1+, -1-) |
|
| 0 |
|
(2+,0+,-2-)(1-,0+,-1+) (1+,0-,-1+) (1+,0+,-1-) (2+, -1+, -1-) (1+, 1-, -2+) |
(2-,0-,-2+) (1+,0-,-1-) (1-,0+,-1-) (1-,0-,-1+) (2-, -1-, -1+) (1-, 1+, -2-) |
|
| -1 |
|
(-2+, -1+, 2-) (-2-, 0+, 1+) (-2+, 0-, 1+) (-2+, 0+, 1-) (-1+, 0+, 0-) (-1+, -1-, 1+) |
(-2-, -1-, 2+) (-2+, 0-, 1-) (-2-, 0+, 1-) (-2-, 0-, 1+) (-1-, 0-, 0+) (-1-, -1+, 1-) |
|
| -2 |
|
(-2+, -1+, 1-) (-2+, 0+, 0-) (-1+, -1-, 0+) (-2+, -2-,2+) |
(-2-, -1-, 1+) (-2-, 0-, 0+) (-1-, -1+, 0-) (-2-, -2+,2-) |
|
| -3 |
|
(-2+, -1+, 0-) (-2+, -2-,1+) |
(-2-, -1-, 0+) (-2-, -2+,1-) |
|
| -4 |
|
|
||
| -5 |
|
|
The next state found is ML =3, MS =1/2, which
is 2F, accounting for 14 microstates (turquoise)
| ML\MS |
|
|
|
|
| 5 |
|
|
||
| 4 |
|
|
||
| 3 |
|
(2+, 1+, 0-)(2+, 2-, -1+) |
(2-, 1-, 0+)(2-, 2+, -1-) |
|
| 2 |
|
(2+, 1+, -1-)(2+, 0+, 0-) (1+, 1-, 0+) (2+, 2-, -2+) |
(2-, 1-, -1+)(2-, 0-, 0+) (1-, 1+, 0-) (2-, 2+, -2-) |
|
| 1 |
|
(2+, 1+, -2-)(2-, 0+, -1+) (2+, 0-, -1+) (2+, 0+, -1-) (1+, 0+, 0-) (1+, 1-, -1+) |
(2-, 1-, -2+)(2+, 0-, -1-) (2-, 0+, -1-) (2-, 0-, -1+) (1-, 0-, 0+) (1-, 1+, -1-) |
|
| 0 |
|
(2+,0+,-2-)(1-,0+,-1+) (1+,0-,-1+) (1+,0+,-1-) (2+, -1+, -1-) (1+, 1-, -2+) |
(2-,0-,-2+)(1+,0-,-1-) (1-,0+,-1-) (1-,0-,-1+) (2-, -1-, -1+) (1-, 1+, -2-) |
|
| -1 |
|
(-2+, -1+, 2-) (-2-, 0+, 1+) (-2+, 0-, 1+) (-2+, 0+, 1-) (-1+, 0+, 0-) (-1+, -1-, 1+) |
(-2-, -1-, 2+) (-2+, 0-, 1-) (-2-, 0+, 1-) (-2-, 0-, 1+) (-1-, 0-, 0+) (-1-, -1+, 1-) |
|
| -2 |
|
(-2+, -1+, 1-) (-2+, 0+, 0-) (-1+, -1-, 0+) (-2+, -2-,2+) |
(-2-, -1-, 1+) (-2-, 0-, 0+) (-1-, -1+, 0-) (-2-, -2+,2-) |
|
| -3 |
|
(-2+, -1+, 0-) (-2+, -2-,1+) |
(-2-, -1-, 0+) (-2-, -2+,1-) |
|
| -4 |
|
|
||
| -5 |
|
|
The next state found is ML =2, MS =1/2, which
is 2D, accounting for 10 microstates (yellow)
| ML\MS |
|
|
|
|
| 5 |
|
|
||
| 4 |
|
|
||
| 3 |
|
(2+, 1+, 0-)(2+, 2-, -1+) |
(2-, 1-, 0+)(2-, 2+, -1-) |
|
| 2 |
|
(2+, 1+, -1-)(2+, 0+, 0-) (1+, 1-, 0+) (2+, 2-, -2+) |
(2-, 1-, -1+)(2-, 0-, 0+) (1-, 1+, 0-) (2-, 2+, -2-) |
|
| 1 |
|
(2+, 1+, -2-)(2-, 0+, -1+) (2+, 0-, -1+)(2+, 0+, -1-) (1+, 0+, 0-) (1+, 1-, -1+) |
(2-, 1-, -2+)(2+, 0-, -1-) (2-, 0+, -1-) (2-, 0-, -1+) (1-, 0-, 0+) (1-, 1+, -1-) |
|
| 0 |
|
(2+,0+,-2-)(1-,0+,-1+) (1+,0-,-1+)(1+,0+,-1-) (2+, -1+, -1-) (1+, 1-, -2+) |
(2-,0-,-2+)(1+,0-,-1-) (1-,0+,-1-)(1-,0-,-1+) (2-, -1-, -1+) (1-, 1+, -2-) |
|
| -1 |
|
(-2+, -1+, 2-) (-2-, 0+, 1+) (-2+, 0-, 1+) (-2+, 0+, 1-) (-1+, 0+, 0-) (-1+, -1-, 1+) |
(-2-, -1-, 2+) (-2+, 0-, 1-) (-2-, 0+, 1-) (-2-, 0-, 1+) (-1-, 0-, 0+) (-1-, -1+, 1-) |
|
| -2 |
|
(-2+, -1+, 1-) (-2+, 0+, 0-) (-1+, -1-, 0+) (-2+, -2-,2+) |
(-2-, -1-, 1+) (-2-, 0-, 0+) (-1-, -1+, 0-) (-2-, -2+,2-) |
|
| -3 |
|
(-2+, -1+, 0-) (-2+, -2-,1+) |
(-2-, -1-, 0+) (-2-, -2+,1-) |
|
| -4 |
|
|
||
| -5 |
|
|
The next state found is another ML =2, MS =1/2,
which is 2D, accounting for 10 microstates (teal)
| ML\MS |
|
|
|
|
| 5 |
|
|
||
| 4 |
|
|
||
| 3 |
|
(2+, 1+, 0-)(2+, 2-, -1+) |
(2-, 1-, 0+)(2-, 2+, -1-) |
|
| 2 |
|
(2+, 1+, -1-)(2+, 0+, 0-) (1+, 1-, 0+)(2+, 2-, -2+) |
(2-, 1-, -1+)(2-, 0-, 0+) (1-, 1+, 0-)(2-, 2+, -2-) |
|
| 1 |
|
(2+, 1+, -2-)(2-, 0+, -1+) (2+, 0-, -1+)(2+, 0+, -1-) (1+, 0+, 0-) (1+, 1-, -1+) |
(2-, 1-, -2+)(2+, 0-, -1-) (2-, 0+, -1-)(2-, 0-, -1+) (1-, 0-, 0+) (1-, 1+, -1-) |
|
| 0 |
|
(2+,0+,-2-)(1-,0+,-1+) (1+,0-,-1+)(1+,0+,-1-) (2+, -1+, -1-) (1+, 1-, -2+) |
(2-,0-,-2+)(1+,0-,-1-) (1-,0+,-1-)(1-,0-,-1+) (2-, -1-, -1+) (1-, 1+, -2-) |
|
| -1 |
|
(-2+, -1+, 2-) (-2-, 0+, 1+) (-2+, 0-, 1+) (-2+, 0+, 1-) (-1+, 0+, 0-) (-1+, -1-, 1+) |
(-2-, -1-, 2+) (-2+, 0-, 1-) (-2-, 0+, 1-) (-2-, 0-, 1+) (-1-, 0-, 0+) (-1-, -1+, 1-) |
|
| -2 |
|
(-2+, -1+, 1-) (-2+, 0+, 0-) (-1+, -1-, 0+) (-2+, -2-,2+) |
(-2-, -1-, 1+) (-2-, 0-, 0+) (-1-, -1+, 0-) (-2-, -2+,2-) |
|
| -3 |
|
(-2+, -1+, 0-) (-2+, -2-,1+) |
(-2-, -1-, 0+) (-2-, -2+,1-) |
|
| -4 |
|
|
||
| -5 |
|
|
The next state found is ML =1, MS =1/2, which
is 2P, accounting for 6 microstates (violet)
| ML\MS |
|
|
|
|
| 5 |
|
|
||
| 4 |
|
|
||
| 3 |
|
(2+, 1+, 0-)(2+, 2-, -1+) |
(2-, 1-, 0+)(2-, 2+, -1-) |
|
| 2 |
|
(2+, 1+, -1-)(2+, 0+, 0-) (1+, 1-, 0+)(2+, 2-, -2+) |
(2-, 1-, -1+)(2-, 0-, 0+) (1-, 1+, 0-)(2-, 2+, -2-) |
|
| 1 |
|
(2+, 1+, -2-)(2-, 0+, -1+) (2+, 0-, -1+)(2+, 0+, -1-) (1+, 0+, 0-)(1+, 1-, -1+) |
(2-, 1-, -2+)(2+, 0-, -1-) (2-, 0+, -1-)(2-, 0-, -1+) (1-, 0-, 0+)(1-, 1+, -1-) |
|
| 0 |
|
(2+,0+,-2-)(1-,0+,-1+) (1+,0-,-1+)(1+,0+,-1-) (2+, -1+, -1-) (1+, 1-, -2+) |
(2-,0-,-2+)(1+,0-,-1-) (1-,0+,-1-)(1-,0-,-1+) (2-, -1-, -1+) (1-, 1+, -2-) |
|
| -1 |
|
(-2+, -1+, 2-)(-2-, 0+, 1+) (-2+, 0-, 1+) (-2+, 0+, 1-) (-1+, 0+, 0-) (-1+, -1-, 1+) |
(-2-, -1-, 2+) (-2+, 0-, 1-) (-2-, 0+, 1-) (-2-, 0-, 1+) (-1-, 0-, 0+) (-1-, -1+, 1-) |
|
| -2 |
|
(-2+, -1+, 1-) (-2+, 0+, 0-) (-1+, -1-, 0+) (-2+, -2-,2+) |
(-2-, -1-, 1+) (-2-, 0-, 0+) (-1-, -1+, 0-) (-2-, -2+,2-) |
|
| -3 |
|
(-2+, -1+, 0-) (-2+, -2-,1+) |
(-2-, -1-, 0+) (-2-, -2+,1-) |
|
| -4 |
|
|
||
| -5 |
|
|
This is all of the terms: 4F (28), 4P (12), 2H (22), 2G (18), 2F (14), 2D (10), 2D (10), 2P (6)
28 + 12 + 22 + 18 + 14 + 10 +10 +6 = 120, so all microstates are accounted for.
To find the J values:
4F ML= 3, MS =3/2 so J = 9/2, 7/2, 5/2, 3/2 and the terms become 4F9/2, 4F7/2, 4F5/2, 4F3/2
4P ML= 1, MS =3/2 so J = 5/2, 3/2, 1/2 and the terms become 4P5/2, 4P3/2, 4P1/2
2H ML= 5, MS =1/2 so J = 11/2, 9/2 and the terms become 2H11/2, 2H9/2
2G ML= 4, MS =1/2 so J = 9/2, 7/2 and the terms become 2G9/2, 2G7/2
2F ML= 3, MS =1/2 so J = 7/2, 5/2 and the terms become 2F7/2, 2F5/2
2D ML= 2, MS =1/2 so J = 5/2, 3/2 and the terms become 2D5/2, 2D3/2
(this is the same for both 2D terms)
2P ML= 1, MS =1/2 so J = 3/2, 1/2 and the terms become 2P3/2, 2P1/2
Energy order predicted by Hund’s rules (less than ½ filled):
4F3/2< 4F5/2< 4F7/2<
4F9/2<4P1/2<
4P3/2<
4P5/2<
2H9/2<
2H11/2<
2G7/2<
2G9/2<
2F5/2<
2F7/2<
2D3/2~
2D3/2<
2D5/2~2D5/2<2P1/2<
2P3/2
For a more quantitative consideration of multielectron systems requires better wavefunctions or the introduction of fudge factors. We convert multielectron systems to hydrogen-like systems by introducing the effective nuclear charge, Z*:
Z* = Z - S
Z* = effective nuclear charge
Z = true nuclear charge
S = screening or shielding constant
Can find S a number of ways: Clementi and Raimondi used accurate numerical calculations to fit S to experiment.
Easier, less quantitatively accurate method is Slater’s: he used the
radial (n) and nodal (l) characteristics
of hydrogenic wavefunctions to establish shielding constants:
Slater’s rules:
1. Write electron configurations according to principal quantum number, grouping s and p orbitals: (1s)(2s2p)(3s3p)(3d)(4s4p)(4d)(4f)...
2. Any electron to the right of the selected electron is ignored (contributes 0 to S)
3. If the electron under consideration is in an (nsnp) group:
a) all other electrons in the same group contribute 0.35/e to S (except 1s, 0.30)
b) all electrons in the n-1 shell contribute 0.85/e to S
c) all electrons in n-2 and lower shells contribute 1.00/e to S
4. If the electron under consideration is in an (nd) or (nf) group:
a) all other electrons in the same group contribute 0.35/e to S
b) all electrons to the left of the selected group contribute 1.00/e to S
Periodic Trends in Z* : Z* increases to the right on the Periodic Table, increases as go down the Periodic Table.