Exercises Advanced Atomic and Molecular Physics WS2011/12

v.Issendorff
3.11.2011

3.) Clebsch-Gordan coefficients hyperfine structure

The Eigenstates of the total angular momentum F can be written in the basis of the j-
and I- states: X
j,I,F
|F, mF , j, Ii = Cm j ,mI ,mF
|j, mj , I, mI i
mj+mI =mF

j,I,F
where Cm j ,mI ,mF
are the Clebsch-Gordan coefficients, which can be taken from the at-
tached table.
a) Describe the Hydrogen states 1s1/2 (F = 0) and 1s1/2 (F = 1) (three mF states) as well
as 2p3/2 (F = 1) (again three states).
b) For the 2p3/2 (F = 1)state additionally break up the j-states into l- and s-states
(again using Clebsch-Coefficients), that is write at least one of the mF -states in the basis
|l, ml , s, ms , I, mI i
(this is an example of the coupling of three angular momenta, which can also be done with
the help of 6j-Symbols)

4.) Helium atom: variational calculation

a) The ground state energy of the helium atom is to be determined by a variational
calculation (Ritz-principle: any change of the wavefunction which lowers the energy brings
you closer to the true solution). We assume that the wavefunction of the two electrons is
a product of hydrogen-like 1s wavefunctions for an effective ion charge Ze :
 3/2
1 Ze Ze r
Ze (r) = e a0
a0

(Ze = 2 would mean that the electrons do not interact at all, Ze = 1 would mean that
each electron sees an ion completely screened by the other electron; the truth will be in
between). We have to determine the effective charge (which is just a parameter of the
wavefunction!) for which the energy expectation value
D E
E = 1Ze 2Ze |H|1Ze 2Ze

is minimal. Here H is the two-electron Hamiltonian:

Ze2 Ze2 e2
H = T1 + T2 +
40 r1 40 r2 40 r12

In the Hamiltonian we have Z = 2 (the true ion charge). The minimal energy E is the
best approximation of the true ground state energy within this Ansatz.
Remark: the expectation value for the first part of the Hamiltonian is easy to calculate, as
these are hydrogen-like operators evaluated for hydrogen-like wavefunctions. The kinetic
energy in a given hydrogen state is always equal to the (absolute value of the ) binding
energy; the potential energy can be easily determined if one rewrites it as
D  Ze2  E Z D Ze  Ze e2  Ze E
1Ze 
 Ze
1 = 1  

40 r1 Ze 40 r1 1

1
For the electron-electron repulsion one gets:
 e2  Z 5 Ze e 2
   
Ze  e
  =
40 r12  8 40 a0

An expression results for the energy which just depends on constants and Ze ; minimizing
this gives the optimum Ze and E.
How close is this to the true ground state energy of helium of E = 79eV?
b) What could one do to improve this result?

2
 20. Clebsch-Gordan coecients 1287

20. CLEBSCH-GORDAN COEFFICIENTS,

SPHERICAL HARMONICS, AND d FUNCTIONS
p p J J ...
Note: A is to be understood over every coecient, e.g., for 8=15 read 8=15. Notation:
M M ...
r m1 m2
Y = 43 cos 
1
1/21/2 +1 1 0 0
+ 1/2 + 1/2 1 0 0
1 21/2 + 5/2 5/2 5/2 3/2
m1 m2 Coefficients
r + 2 1/2 1 3/2 + 3/2
. .
+ 1/2 1/2 1/2 1/2 1
1/2 + 1/2 1/2 1/2 1
3
Y11 = 8 sin  ei
. .
+ 2 1/2 1/5 4/5 5/2 3/2 . .
1/2 1/2 1 + 1 + 1/2 4/5 1/5 + 1/2 + 1/2
r  
5 3
Y20 = 4 2 cos2  2 1 + 1 1/2 2/5 3/5 5/2 3/2
0 + 1/2 3/5 2/5 1/2 1/2
11/2 + 3/2 r 0 1/2
Y21 = 815 sin  cos  ei
3/2 3/2 1/2 3/5 2/5 5/2 3/2
+ 1 + 1/2 1 + 1/2 + 1/2 1 + 1/2 2/5 3/5 3/2 3/2
+ 1 1/2
2 1 1/2 4/5 1/5 5/2
1/3 2/3 3/2 1/2
r 3/21/2 + 2 2 1 2 + 1/2 1/5 4/5 5/2
Y22 = 14 215 sin2  e2i
0 + 1/2 2/3 1/3 1/2 1/2
+ 3/2 +1/2 1 + 1 + 1 2 1/2 1
0 1/2 2/3 1/3 3/2
1 + 1/2 1/3 2/3 3/2 + 3/2 1/2 1/4 3/4 2 1
+ 1/2 + 1/2 3/4 1/4 0 0
21 3 1 1/2 1 5/2
+3 3 2 3/21 + 5/2 5/2 3/2
+ 1/2 1/2 1/2 1/2 2 1
+2 +1 1 +2 +2 + 3/2 + 1 1 + 3/2 + 3/2 1/2 + 1/2 1/2 1/2 1 1
+ 2 0 1/3 2/3 3 2 1 + 3/2 0 2/5 3/5 5/2 3/2 1/2 1/2 1/2 3/4 1/4 2
+ 1 + 1 2/3 1/3 +1 +1 +1 + 1/2 + 1 3/5 2/5 + 1/2 + 1/2 + 1/2 3/2 + 1/2 1/4 3/4 2
+ 2 1 1/15 1/3 3/5 + 3/2 1 1/10 2/5 1/2 3/2 1/2 1
11 + 22 2 1 + 01 + 01 8/15 1/6 3/10
6/15 1/2 1/10
3 2 1 + 1/2 0 3/5 1/15 1/3 5/2 3/2 1/2
0 0 0 1/2 + 1 3/10 8/15 1/6 1/2 1/2 1/2
+1 +1 1 +1 +1
+ 1 1 1/5 1/2 3/10 + 1/2 1 3/10 8/15 1/6
+ 1 0 1/2 1/2 2 1 0 0 0 3/5 0 2/5 3 2 1 1/2 0 3/5 1/15 1/3 5/2 3/2
0 + 1 1/2 1/2 0 0 0 1 + 1 1/5 1/2 3/10 1 1 1 3/2 + 1 1/10 2/5 1/2 3/2 3/2
+ 1 1 1/6 1/2 1/3 0 1 6/15 1/2 1/10 1/2 1 3/5 2/5 5/2
0 0 2/3 0 1/3 2 1 1 0 8/15 1/6 3/10 3 2 3/2 0 2/5 3/5 5/2
1 + 1 1/6 1/2 1/3 1 1 2 + 1 1/15 1/3 3/5 2 2 3/2 1 1
0 1 1/2 1/2 2 1 1 2/3 1/3 3
Y` m = ( 1)mY`m 1 0 1/2 1/2 2 r 2 0 1/3 2/3 3 hj1j2 m1m2 jj1 j2 JM i
1 1 1 d`m;0 = 2`4+ 1 Y`m e im 2 1 1 = ( 1)J j1 j2 hj2 j1 m2 m1 jj2 j1 JM i

djm ;m = ( 1)m m djm;m = dj m; m

0
3/23/2 3
+3 3
1=2
d = cos 2 d11==22; 1=2 = sin 2
1=2;1=2
0 0 0
2
+ 3/2 + 3/2 1 +2 +2

d11;1 = 1 + 2cos  p
d11;0 = sin
23/2 7/2
+ 7/2 7/2 5/2
+ 3/2 + 1/2 1/2 1/2 3 2 1
+ 1/2 + 3/2 1/2 1/2 + 1 + 1 +1
+ 2 + 3/2 1 + 5/2 + 5/2
+ 3/2 1/2 1/5 1/2 3/10 2
+ 2 + 1/2 3/7 4/7 7/2 5/2 3/2 + 1/2 + 1/2 3/5 0 2/5 3 2 1 0
+ 1 + 3/2 4/7 3/7 + 3/2 + 3/2 + 3/2
d11; 1 = 1 2cos 
1/2 + 3/2 1/5 1/2 3/10 0 0 0 0
+ 2 1/2 1/7 16/35 2/5 + 3/2 3/2 1/20 1/4 9/20 1/4
+ 1 1/2 4/7 1/35 2/5 7/2 5/2 3/2 1/2
+ 1/2 1/2 9/20 1/4 1/20 1/4
22 44 0 3/2 2/7 18/35 1/5 + 1/2 + 1/2 + 1/2 + 1/2 1/2 + 1/2 9/20 1/4 1/20 1/4 3 2 1
d10;0 = cos 
4 3
+2 3/2 1/35 6/35 2/5 2/5 3/2 + 3/2 1/20 1/4 9/20 1/4 1 1 1
+2 +2 1 +3 +3
+1 1/2 12/35 5/14 0 3/10 + 1/2 3/2 1/5 1/2 3/10
+2 +1 1/2 1/2 4 3 2 1/2 18/35 3/35 1/5
+1 +2 1/2 1/2 + 2 +2 +2
0 1/5 7/2 5/2 3/2 1/2 1/2 1/2 3/5 0 2/5 3 2
1 3/2 4/35 27/70 2/5 1/10 1/2 1/2 1/2 1/2 3/2 + 1/2 1/5 1/2 3/10 2 2
+2 0 3/14 1/2 2/7 + 1 3/2 4/35 27/70 2/5 1/10
+1 0 3/7 1/2 3/2 1/2 1/2 3
1 4/7 4 3 2 1 0 1/2 18/35 3/35 1/5 1/5
0 2 3/14 1/2 2/7 +1 +1 +1 +1 1 1/2 12/35 5/14 3/2 1/2 1/2 1/2 3
0 3/10 7/2 5/2 3/2
+ 2 1 1/14 3/10 3/7 1/5 2 3/2 1/35 6/35 2/5 2/5 3/2 3/2 3/2 3/2 3/2 1
+ 1 0 3/7 1/5 1/14 3/10 0 3/2 2/7 18/35 1/5
0 1 3/7 1/5 1/14 3/10 4 3 2 1 0 1 1/2 4/7 1/35 2/5 7/2 5/2
1 2 1/14 3/10 3/7 1/5 0 0 0 0 0
2 1/2 1/7 16/35 2/5 5/2 5/2
+ 2 2 1/70 1/10 2/7 2/5 1/5 1 3/2 4/7
d33==22;3=2 = 1 + 2cos  cos 2
3/7 7/2
+ 1 1 8/35 2/5 1/14 1/10 1/5 2 1/2 3/7 4/7 7/2
0 0 18/35 0 2/7 0 1/5
2 3/2
p 1 1 8/35 2/5 1/14 1/10 1/5
d33==22;1=2 = 3 1 + 2cos  sin 2
4 3 2 1 1
2 2 1/70 1/10 2/7 2/5 1/5 1 1 1 1
 2
d22;2 = 1 + 2cos 
+ 1 2 1/14 3/10 3/7 1/5
p
d33;=22; 1=2 = 3 1 2cos  cos 2
0 1 3/7 1/5 1/14 3/10
1 0 3/7 1/5 1/14 3/10 4 3 2
1 + cos  2 1 1/14 3/10 3/7 1/5 2 2 2

d33;=22; 3=2 = 1 2cos  sin 2 d22;1 =

p 2
sin 
d21;1 = 1 + 2cos  (2 cos  1)
0 2 3/14 1/2 2/7
1 1 4/7 0 3/7 4 3

d22;0 = 46 sin2 
2 0 3/14 1/2 2/7 3 3
d31==22;1=2 = 3 cos2 1 cos 2
r
d21;0 = 32 sin  cos 
1 2 1/2 1/2 4
2 1 1/2 1/2 4
1 cos 
d31==22; 1=2 = 3 cos2 + 1 sin 2 d22; 1 = sin    2 2 1
2
 1 cos  2 d21; 1 = 1 2cos  (2 cos  + 1) d20;0 = 23 cos2  12
d22; 2 = 2
Figure 20.1: Sign convention is that of Wigner (Group Theory, Academic Press, New York, 1959), also used by Condon and Shortley (The
Theory of Atomic Spectra, Cambridge Univ. Press, New York, 1953), Rose (Elementary Theory of Angular Momentum, Wiley, New York, 1957),
and Cohen (Tables of the Clebsch-Gordan Coecients, North American Rockwell Science Center, Thousand Oaks, Calif., 1974). The signs and
numbers in the current tables have been calculated by computer programs written independently by Cohen and at LBL.