Quantum Mechanics 2
Problem set 8
1. The Hamiltonian is
X p2i Ze e2
H= − + .
i 2m ri |~x1 − x~2 |
Ignoring the spin part for now, our initial guess for the ground state is the product
of two Hydrogen ground states |100i |100i, and we turn the charge number Z to a
parameter (reasononig as given in the worksheet). So, explicitly
3/2
1 Z∗
(Z ∗ ) ∗ r/a
ψ100 = √ e−Z 0
π a0
is the one particl function, and our guess is including the spin
|ψi = |100i |100i |00i .
The wave function is properly normalized, so all there is left to do is to minimize
hψ| H |ψi with respect to Z. Due to the form of the Hamiltonian as two hydrogen-
like Hamiltonians and an interaction, one can write
e2 (Z − Z ∗ ) e2
hψ| H |ψi = 2E − 0(Z) − 2 hψ| |ψi + hψ| |ψi
|~x1 | |~x1 − x~2 |
with
E0 (Z ∗ ) = −Ry Z ∗ 2 .
Use also
e2 Z ∗ (Z − Z ∗ ) ∗
∗ 2 (Z − Z )
hψ| |ψi = 2Ry Z
|~x1 | Z∗ Z∗
e2 5
hψ| |ψi = Ry Z ∗
|~x1 − x~2 | 4
to get
5
∗2
hψ| H |ψi = −2Ry −Z + 2z Z − Z ∗ .
∗
8
Its minimum is at
5
Z∗ = Z − ,
16
which gives
2 !
525
E0 = Ry −2Z Z − 2 ≈ −77.48 eV
4 16
compared with the experimental value of −78.97 eV .
1
2. (a) We first write the state explicitly
1
|ψi = √ (|100i |2lmi |↑↓i − |2lmi |100i |↓↑i) .
2
Under the exchange of the two particles the new state is
E 1
ψ̃ = √ (|2lmi |100i |↓↑i − |100i |2lmi |↑↓i) = − |ψi .
2
so the Pauli principle is satisfied.
(b) Remember that
√
|↑↓i = (|10i + |00i) / 2
√
|↓↑i = (|10i − |00i) / 2
so
1
S 2 |ψi = 2 √ (|100i |2lmi − |2lmi |100i) |10i =
6 λ |ψi
2
The previous reasoning claiming that therefore this is not an eigenstate of H0
(unperturbed) was wrong.
(c) Remember that there is only one way to add |lmi and |00i to form |LM i
|lmi |00i = |l0, L = l, M = mi
|00i |lmi = |0l, L = l, M = mi
but
L2 |l0, L = l, M = mi = l(l + 1) |l0, L = l, M = mi
L2 |0l, L = l, M = mi = l(l + 1) |0l, L = l, M = mi
and similarly for Lz . One gets
1
|ψi = √ (|n1 = 1, n2 = 2, 0l, L = l, M = mi |↑↓i − |n1 = 2, n1 = 2, l0, L = l, M = mi |↓↑i)
2
which is an eigenstate of L2 , Lz . The state is also an eigenstate of Sz with
eigenvalue 0 (since Ms = ms,1 + ms,2 ).
(d) Once the state is written that way, it is obvious that
1
|ψi = √ (|n1 = 1, n2 = 2, 0l, L = l, M = mi |↓↑i − |n1 = 2, n1 = 2, l0, L = l, M = mi |↑↓i)
2
is also an eigenstate of L2 , Lz , Sz , with the same eigenvalues.
2
3. The state ϕi (~xi )χi (msi ) is orthogonal to all states with msj 6= msi . The spatial
wave functions ϕj with msi = msj all satisfy a Schrödinger equation with exactly
the same potential
h̄2 2
!
Z
− ∇ + u(x) ϕi (x) + dx0 u(x, x0 )ϕi (x0 ) = εi ϕi (x).
2m
with
−e2
u(x, x0 ) = ϕ∗j (x0 ) ϕj (x) = u(x0 , x)∗ .
X
j |x − x0 |
dxϕ∗j (x)
R
Multiply this by and get
h̄2 2
Z !Z Z Z
dxϕ∗j (x) − ∇ + u(x) ϕi (x)+ dx dx0 u(x, x0 )ϕ∗j (x)ϕi (x0 ) = εi dxϕ∗j (x)ϕi (x).
2m
Subtracting from that the equation with i ↔ j and using Hermiticity, one finds
hϕj | ϕi i = δij
4. The other contributions to W other than Wdd involve products of two multipole
moments, one relative to each atom, and at least one of which is of order higher
than 1. But the first order correction is of the form (for each atom) h100| Tq(k) |100i,
and a multipole of order higher than 1 means k > 1. According to th Wigner-
Eckart theorem the correction will be proportional to the Clebsh-Gordan coefficient
(0k0q| 00) which vanishes.
5. I assume you all have the tables with solution from previous years. I am going to
find the spectral terms a little differently. Since we are given a configuration, nd2 ,
we know that there are 2 electrons with l = 2 (m = −2 . . . 2), so they can add to
L = 0 . . . 4 and spin up and down, that
! can add to S = 0, 1. The total number of
10
possible configurations is then = 45.
2
We start by considering the maximal state both with m = 2, so that M = 4, and
therefore L = 4. Since both are in the same state, their spin must be opposite, (and
since the wave function must be antisymmetric it must belong to the singlet), so
there is only one possible arrangement for this (M = 4, MS = 0).
We can get M = 3 by m = 2, 1 with m = 1, 2 (these are not distinct). Since they
have different m, their spin can add to MS = −1, 0, 1 i.e. 4 spin options, giving
total of 4 options. The singlet option correspond to the L = 4 multiplet, and the 3
triplet then correspond to the L = 3 multiplet.
Now, M = 2, is obtained by m = 2, 1, 0 with m = 0, 1, 2. When both are in m = 1,
their spin must be antiparallel, which means MS = 0, of either S = 0 (singlet), or
3
of S = 1 (triplet). For the other m1 6= m2 possibilities, their spin can again add to
MS = −1, 0, 1 ainglet + triplet. One singlet state belongs to the L = 4 multiplet,
3 triplet to the L = 3 multiplet(with their spin belonging to the S = 1 multiplet),
and the other singlet to the L = 2 multiplet, total 5 states.
M = 1 is obtained by m = 2, 1 and m = −1, 0 times four spin states (3 triplet +
1 singlet as usual), giving a total of 8 possibilities. One (singlet) belongs to L = 4
(spin singlet), 3 to L = 3, 1 to L = 2, 3 to L = 1.
Remember that for M = −1 . . . − 4, the same considarations exactly lead to the
same number of states for each M .
For M = 0, we can get by m = 2, 1, 0 with m = −2, −1, 0. The m = 0’s must take
MS = 0, and the rest two options can take one of the four spin states, total 9 states.
Summing all: 9 + 2 × (1 + 4 + 5 + 8) = 45 states as desired. The spectral terms then
will be 1 G, 3 F, 1 D, 3 P, 1 S