Comments to lecture 5: Wave function of hydrogen when considering spin-orbit coupling.

The good states are linear combinations of original states with quantum numbers of
l, ml , s, ms . To write |jmj i (for given l and s) as a linear combination of |lml i|sms i we
would use the appropriate Clebsch-Gordan coefficients (in Chapter 4).
For example, for n = 2, l = 1, j = 3/2, mj = 1/2,
r
r
1
1
1
2
1 1
3 1
i=
|1 1i| i +
|10i|
i.
|
2 2
3
2
2
3
2 2

In notation of nlm and (s):

r
=

1
1
211 ( ) +
3
2

2
1
210 ( )
3
2

LECTURE 6 ATOMS

For an atom of atomic number Z, the Hamiltonian is


 2

X
Z
Z 
X
1
Ze
1
e2
1
~2 2
.
j
H=
+

2m
40
rj
2 40 j6=k |rj rk |
j=1
|
{z
} |
{z
}
jth electron

(1)

mutual repulsion

The problem is to solve Schrodinger equation H = E for the wave function (r1 , r2 , . . . , rZ ).
Because electrons are identical fermions, the complete state (position and spin),
(r1 , r2 , . . . , rZ )(s1 , s2 , . . . , sZ ),

(2)

is antisymmetric with respect to interchange of any two electrons. In particular, no two

electrons can occupy the same state.
Unfortunately, the Schrodinger equation with Hamiltonian of equation (1) can not be
solved exactly, except for Z = 1 (hydrogen). In practice, we resort to approximation methods.
6.1 Helium


 

~2 2
1 2e2
1 2e2
e2
~2 2
1
H=
1
2
.
+
+
2m
40 r1
2m
40 r2
40 |r1 r2 |

(3)

The Hamiltonian consists of two hydrogenic Hamiltonians (with nuclear charge 2e), and a
term of the repulsion between two electrons. The last repulsion term causes all the trouble.
If we simply ignore it, the Schrodinger equation separates, and the solution is just products
of two hydrogen wave functions:
(r1 , r2 ) = nlm (r1 )n0 l0 m0 (r2 ),

(4)

only with half the Bohr radius, and four times the Bohr energies. The total energy would
be
E = 4(En + En0 ),

(5)

where En = 13.6/n2 eV. In particular, the ground state would be

0 (r1 , r2 ) = 100 (r1 )100 (r2 ) =
2

8 2(r1 +r2 )/a

e
,
a3

(6)

and its energy would be

E0 = 8(13.6 eV) = 109 eV.

(7)

Note: electrons are fermions, so the complete state wave function has to be antisymmetric. That means, for the position state and spin state, one has to be
symmetric and the other antisymmetric (so the product of the two is antisymmetric).

Figure 1. Energy level diagram for helium. The numerical values on the vertical scale are relative
to the ground state of ionized helium (He+ : 4(-13.6) eV = -54.4 eV.)

Because 0 is a symmetric (symmetric under exchange of two particles, which you can see
clearly from equation 6) function, the spin state has to be antisymmetric, so the ground state
of helium should be a singlet configuration, with the spins oppositely aligned. The actual
ground state of helium is indeed a singlet, but the energy is -78.975 eV. This discrepancy
comes from electron repulsion, which we ignored in the above calculation. It is clearly
positive, and brings the total energy from -109 eV to -79 eV.
The excited state of helium consist of one electron in the hydrogenic ground state, and
the other in an excited state:
nlm 100 .

(8)

If you put both electrons in excited states, one immediately drops to the ground state,
releasing enough energy to knock the other one into the continuum (E > 0), leaving you
with a helium ion and a free electron. We can construct both symmetric and antisymmetric
combinations,
(r1 , r2 ) = A[nlm (r1 )100 (r2 ) 100 (r1 )nlm (r2 )].

(9)

The plus sign go with the antisymmetric spin configuration (the singlet), and they are
called parahelium; the minus sign go with the symmetric spin configuration (the triplet),
and they are known as orghohelium. The symmetric spatial state brings the electrons
closer together, we expect a higher interaction energy in parahelium, which is experimentally
confirmed (Figure 1). The ground state is parahelium.
6.2 Periodic Table
One-particle hygrogenic states (n, l, m), are called orbitals. There are n2 states for a
given n, so 2, 8, 18, 32, 50, . . . electrons for different shells starting with n = 1. Of course, we
also have to take into account the electron-electron interactions. The Periodic Table can
be constructed according to the electron configurations of atoms - we need to fill electrons
to all the states from lowest energy to higher energies.
With helium, the n = 1 shell is filled. Lithium (Z = 3) has to put one electron into
the n = 2 shell. In the absence of electron-electron interactions, both l = 0 and l = 1
have the same energy. But the effect of electron repulsion is to favor the lowest value of
l: higher angular momentum (higher l value) throw the electron outward further, the inner
electrons screen the nucleus more effectively, so the energy is higher. So lithiums 3rd
4

electron occupies orbital (2,0,0). Beryllium (Z = 4) fits the 4th electron to (2,0,0) too with
opposite spin, but boron (Z = 5) has to use (2,1,0). Continuing this way, we can finish the
second line of the periodic table to neon (Z=10).
For the n = 3 shell, there are two atoms (sodium and magnesium) with l = 0, and six
with l = 1 (aluminum through argon). Following argon there should be 10 atoms with
l = 2; however, the screening effect is so strong that it overlaps the next shell, so potassium
and calcium choose n = 4, l = 0. After that, we get back to pick up the n = 3, l = 2
stragglers, followed by n = 4, l = 1 (Figure 2).
Some notations: Sharp, Principle, Diffuse, Fundamental, g, h, i, k, l for l = 0, 1, 2, 3, 4, 5 . . . .
Electron configuration
(1s)2 (2s)2 (2p)2

(10)

tells us that there are two electrons in the orbital (1,1,0), two in the orbital (2,0,0) and two
in some combination of the orbitals (2,1,1), (2,1,0), and (2,1,-1). This is the ground state of
carbon.
In the above example, the two electrons have orbital angular momentum quantum number
1, so the total angular momentum quantum number, L, could be 2, 1, or 0. Meanwhile,
the two (1s) electrons are locked together in the singlet state, with total spin zero, so are
the two (2s) electrons. The two (2p) electrons could be in the singlet configuration or the
triplet configuration, so the total spin quantum number S could be 1 or 0. The grand total
(orbital plus spin) J could be 3, 2, 1, or 0. The Hunds rules can be used to figure out the
ground state. New notations:
2S+1

LJ ,

(11)

Hunds rule, Problem 5.13

(a) 1st: The state with the highest total spin (S) will have the lowest energy.
(b) 2nd: For a given spin, the state with the highest total orbital angular momentum
(L), consistent with overall antisymmetrization, will have the lowest energy.
(c) 3rd: If a subshell (n, l) is no more than half filled, then the lowest energy level has
J = |L S|; if it is more than half filled, then J = L + S has the lowest energy.
The easy to follow procedure:
(1) Make as many spins as possible parallel, then compute ms and call that S.
5

(2) Now set the orbital states to make maximum ml , and call this L, but dont allow any
two electrons to be in the same state (of ms and ml ).
(3) If the shell is more than half full, pick the highest total angular momentum state
J = L + S, otherwise pick the lowest J = |L S|.
Example: Nitrogen. Three 2p electrons are all in spin up states (ms = 1/2), so S = 3/2.
Their ml have to be 1, 0, -1 respectively, so L = 0. J = 3/2. The ground state is 4 S3/2 .
Example: Oxygen, with Z = 8 has the 1s and 2s levels filled giving j = 0 as a base. It
has four valence 2p electrons which we will treat as two valence 2p holes. Hunds first rule,
maximum total S, tells us to couple the two hole spins to S = 1. This is the symmetric spin
state so well need to make the space state antisymmetric. Hunds second rule, maximum
L, doesnt play a role because only the L = 1 state is antisymmetric. Since the shell is more
than half full we couple to the the highest J = L + S = 2. So the ground state is 3 P2 .

Figure 2. Application of Hunds rule for oxygen ground state.

Figure 3. Ground state electron configurations for the first four rows of the Periodic Table.