Department of Physics Temple University

Quantum II, 5702 Instructor: Z.-E. Meziani

Homework # 4

Friday, October 14, 2016

Textbook: Claude Cohen Tannoudji, Bernard Diu and Franck Laloë, Second Volume

Complement HXI

Exercise 1, page 1200

A particle of mass m is placed in an infinite one-dimensional well of width a:

V (x) = 0 for 06x6a

V (x) = +∞ elsewhere (1)

It is subject to a perturbation W of the form:

 a
W (x) = aw0 δ x − (2)
2
Where w0 is a real constant with the dimensions of an energy.
a. Calculate, to first order in w0 , the modifications induced by W (x) in the energy levels of the particle.
Solution (a): The energy levels and wave functions for the infinite well potential described above are given by
r
~2 π 2 2 2  nπx 
En = 2
n , ψn (x) = sin (3)
2ma a a
According to perturbation theory, the energy of the nth state is given to first-order by

~2 π 2
En = + En(1) (4)
2ma2
where

2 a 2  nπx 
Z
En(1) =< ψn |W (x)|ψn > = sin W (x)dx (5)
a 0 a
2 a 2  nπx 
Z  a
= sin aw0 δ x − dx (6)
a 0 a 2
2  nπ 
= × aw0 sin2 (7)
a  nπ  2
= 2w0 sin2 (8)
2
Hence depending on wether the quantum number is odd or even the energies are given following:

~2 π 2 2
En = n + 0 if n is even (9)
2ma2
+ 2w0 if n is odd (10)

1
 p
b. Actually, the problem is exactly soluble. Setting k = 2mE/~2 , show that the possible values of the
energy are given by one of the two equations sin(ka/2) = 0 or tan(ka/2) = −~2 k/maw0 ( watch out
for the discontinuity of the derivative of the wave function at x = a/2).
Solution(b): The Schrödinger equation

d2 ψ(x) 2maw0 2mE

+ δ(x − a/2)ψ(x) + 2 ψ(x) = 0 (11)
dx2 ~2 ~
reduces for the case x 6= a/2 to
d2 ψ(x) 2mE
+ 2 ψ(x) = 0 (12)
dx2 ~
The solutions of this equation must also vanish at the boundaries where the potential is infinite, namely
x = 0 and x = a

ψL (x) = A sin kx 0 6 x < a/2 (13)

ψR (x) = B sin k(x − a) a/2 < x 6 a (14)
p
where k = 2m|E|/~2 . The continuity of the wave function at x = a/2 requires ψL (x/2) = ψR (a/2)
which leads to A sin (a/2) = −B sin (a/2) and hence A = −B. The solution is given by

ψL (x) = A sin kx 0 6 x < a/2 (15)

ψR (x) = −A sin k(x − a) a/2 < x 6 a (16)

The energy eigenvalues are obtained from the discontinuity condition of the first derivative of the wave
function obtained by integrating Eq. 11. from a/2 −  to a/2 + 

 
dψR (x) dψL (x) 2maw0  a 
lim |x=a/2+ − |x=a/2− + ψ =0 (17)
→0 dx dx =0 ~2 2

Evaluating the derivatives and taking the limit  = 0 we find.

h a i h a i 2maw0  a
−kA cos k − a − kA cos +A sin k =0 (18)
2 2 ~2 2
leading to
 a ~2 k
tan k = (19)
2 maw0
c. Discuss the results obtained with respect to the sign and size of w0 . In the limit w0 −→ 0, show that
one obtains the results of question a).
Solution(c):

Exercise 5, page 1203

b~
Consider a system of angular momentum J. We confine ourselves in this problem to a three dimensional
subspace spanned by the three kets {| + 1 >, |0 >, | − 1 >}, common eigenstates of Jˆ2 (eigenvalues 2~2 ) and
Jˆz (eigenvalues +~, 0 ,−~). The Hamiltonian of the system is :

b
Ĥ0 = aJˆz + Jˆz2 (20)
~
where a and b are two positive constants, which have the dimensions of an angular frequency.

2
a. What are the energy levels of the system? For what values of the ratio b/a is there degeneracy?
Since {| + 1 >, |0 >, | − 1 >} are eigenstates of Jˆz and Jˆz2 they are also eigenstates of Ĥ0 .

Ĥ0 |+ > = = ~ (a + b) |+ >

Ĥ0 |0 > = = 0 × |0 >
Ĥ0 |− > = = ~ (−a + b) |− > (21)

The energy eigenvalues for the eignenstates | + 1 >, |0 > and | − 1 > are E+ , E0 and E− respectively
where

E+ = ~ (a + b)
E0 = 0
E− = ~ (b − a) (22)

When b/a = 1 both |0 > and |− > are eigenstates of Ĥ0 corresponding to the same eigenvalue namely
E0 = E− = 0
~ 0 is applied in a direction ~u with polar angles θ and φ. The interaction with
b. A static magnetic field B
~
B0 of the magnetic moment of the system:
~ = γ J~
M (23)

(γ: the gyromagnetic ratio, assumed to be negative) is described by the Hamiltonian:

W = ω0 Ju (24)

where ω0 = −γ|B ~ 0 | is the Larmor angular frequency in the field B ~ 0 , and Ju is the component of J~ in
the ~u direction:
Jˆu = Jˆz cos θ + Jˆx sin θ cos φ + Jˆy sin θ sin φ (25)
Write the matrix which represents Ŵ in the basis of the three eigenstates of H0 .
We can write the matrix of Ŵ by writing down the matrices of Jˆz , Jˆx and Jˆy in the basis {| + 1 >
, |0 >, | − 1 >} and then form the matrix Ŵ = ω0 Jˆu . Jˆz is obviously diagonal in this basis but Jˆx and
Jˆy can be written using their expression in terms of Jˆ+ and Jˆ− . We find

     
0 1 0 0 −i 0 1 0 0
1  1 
Jx = ~ √ 1 0 1 , Jy = ~ √ i 0 −i  , Jz = ~  0 0 0  (26)
2 0 1 0 2 0 i 0 0 0 −1

This leads to
   
cos θ 0 0 0 sin θ cos φ 0
~ω
 + √ 0  sin θ cos φ
Ŵ = ~ω0  0 0 0 0 sin θ cos φ 
0 0 − cos θ 2 0 sin θ cos φ 0
 
0 −i sin θ cos φ 0
~ω0
+ √  sin θ cos φ 0 −i sin θ cos φ 
2 0 sin θ cos φ 0
1
 
cos θ √ [cos φ − i sin φ] sin θ 0
2
= ~ω0  √12 [cos φ + i sin φ] sin θ
 0 √1 e−iφ sin θ 
2 
0 √1 e−iφ sin θ − cos θ
2
e−iφ sin θ
 
cos θ 0
1
= ~ω0 √  e+iφ sin θ 0 e−iφ sin θ 
2 0 iφ
e sin θ − cos θ

3
c. Assume that b = a and the ~u direction is parallel to Ox. We also have ω0  a. Calculate the
energies and eigenstates of the system, to first order in ω0 for the energies and the zeroth order for the
eigenstates.
In the case where b = a the Hamiltonian Ĥ0 matrix would read:
 
2a 0 0
Ĥ0 = ~  0 0 0  (27)
0 0 0

and for θ = π/2 and φ = 0 The matrix of Ŵ would reads:

 
0 1 0
1 
Ŵ = ~ω0 √ 1 0 1  (28)
2 0 1 0
The complete hamiltonian with the interaction energy takes the form
 √ a 
2 2 1 0
1  ω0
Ĥ = ~ω0 √  (29)

2 1 0 1 
0 1 0

The characteristic equation to find the eigenvalues reads:

 
 2~a − λ √1 ~ω0 0  2
2
    
 √1 ~ω √1 ~ω0 2 ~ω0 ~ω0 ~ω0
 2 0 −λ 2  = (2~a − λ)[(−λ ) − √

] − √ [(−λ) √ ] = 0

 0 √1 ~ω0 −λ

 2 2 2
2

Solving for the eigenvalues this way proves to be very cumbersome. An easier way to go about it by
hand is by diagonalizing the subspace
 √ 
√−λ 2~ω0
2~ω0 −λ

Doing this gives us eigenvalues λ = ± ~ω

√ 0 and the following diagonalized matrix:
2
√ !
2
2 ~ω 0 √
0
0 − 22 ~ω0

We can now insert this back into the Ĥ matrix and solve for the eigenvalues:
√1 ~ω0
 
 2~a − λ 0  √ ! √ !
√ 2

 √1 2
 2 2
2 ~ω0 − λ 0  = (2~a − λ)[− ~ω0 − λ ~ω0 + λ ]

2
~ω0
2 2

 √ 
2
 0 0 − 2 ~ω0 − λ 
  √ !
1 1 2
− √ ~ω0 [ √ ~ω0 − ~ω0 − λ ]
2 2 2
√ ! √ !
2 2
= −(2~ − λ)[ ~ω0 − λ ~ω0 + λ ]
2 2
  √ !
1 1 2
+ √ ~ω0 [ √ ~ω0 ~ω0 + λ ]
2 2 2
√ ! √ !
2 2 1
= ~ω0 + λ [(2~a − λ) ~ω0 − λ + ~2 ω02 ]]
2 2 2

4
 √
2
Setting this equal to zero yields eigenvalues λ1 = − 2 ~ω0 and
√ √ s
2 2 ω0 3 ω02
λ± = (~a + ~ω0 ) ± ~a 1 − −
4 2 a 8 a2
Using ω0  a:
√ √  !
2 2 ω0
λ± ≈ (~a + ~ω0 ) ± ~a 1 −
4 4 a
√
2
This simplifies to eigenvalues λ2 = 2~a and λ3 = 2 ~ω0

d. Assume that b = 2a and that we again have ω0 << a, the direction of u now being arbitrary. In the
{| + 1 >, |0 >, | − 1 >} basis, what is the expansion of the ground state |ψ0 > of H0 + W , to first order
in ω0 ? The energy eigenvalues are now:

E+ = 3a~
E0 = 0
E− = a~

The Hamiltonian Ĥ0 matrix would read:

 
3a 0 0
Ĥ0 = ~  0 0 0  (30)
0 0 a

The total Hamiltonian Ĥ with u now being arbitrary is the sum of Ĥ0 plus the interaction energy W :
ω0 −iφ
 
3a + ω0 cos(θ) √ 2
e sin(θ) 0
 ω ω0 −iφ
Ĥ = ~  √02 eiφ sin(θ) 0 √
2
e sin(θ) 

ω0 iφ
0 √
2
e sin(θ) a − ω0 cos(θ)

We can find the exact solution by diagonalizing the total Hamiltonian matrix and solving for the
eigenvalues:
√ 0 e−iφ sin(θ)
 
 3a~ + ω0 ~ cos(θ) − λ ~ω 0 
 2 
√ 0 eiφ sin(θ)
~ω
−λ √ 0 e−iφ sin(θ)
~ω
=0
 
 2 2
√ 0 eiφ sin(θ)
~ω

− −

 0 2
a~ ~ω 0 cos(θ) λ 

One can compare this to the general expression for the expansion of the ground state |ψ0 > according
to perturbation theory:
X < ϕm |Ŵ |ϕn >
|ψn > = |ϕn > + (0) (0)
|ϕm >
En − Em
< −1|Ŵ |0 > < 1|Ŵ |0 >
|ψ0 > = |0 > − |−1>− |1 >
a~ 3a~

Plugging in the following matrix elements:

~ω0 iφ
< −1|Ŵ |0 > = √ e sin(θ)
2
~ω0 −iφ
< 1|Ŵ |0 > = √ e sin(θ)
2

Gives us the expansion of the ground state, consistent with the exact solution:
ω0 eiφ sin(θ) ω0 e−iφ sin(θ)
|ψ0 >= |0 > − √ |−1>− √ |1 >
2a 3 2a

5
 Calculate the mean value < M > of the magnetic moment
P M of the system in the state |ψ0 >. Are
< M > and B0 parallel? Use M = γJ where J = Ji î where i = x, y, z. We need to calculate
< ψ0 |γJ||ψ0 >:

ω0 eiφ sin(θ) ω0 e−iφ sin(θ)

< 0|γJi |0 > − < 0|γJi | √ | − 1 > − < 0|γJi | √ |1 >
2a 3 2a

The < 0|Ji |0 > terms vanish. Referring back to the Jx , Jy , and Jz matrices allows one to determine
the following matrix elements:
√
2~
< 0|Jx | − 1 > =
2√
−i 2~
< 0|Jy | − 1 > =
√ 2
2~
< 0|Jx |1 > =
√2
i 2~
< 0|Jy |1 > =
2

Plugging in these values for each component of < γJ > yields:

 
~ω0 γ 2 2
< γJ > = − sin(θ) cos(φ)x̂ − sin(θ) sin(φ)ŷ + 0ẑ
a 3 3
= <M>

Since there is no z-component

P of the magnetic moment, it is not parallel to B0 . Show that one can
write: < Mi > = χij Bj with i = x, y, z. Calculate the coefficients χij (the components of the
susceptibility tensor). Expressing Bx , By , and Bz in spherical coordinates, the sum can be expanded
as follows:

< Mx > = χxx B0 sin(θ) cos(φ) + χxy B0 sin(θ) sin(φ) + χxz B0 cos(θ)
< My > = χyx B0 sin(θ) cos(φ) + χyy B0 sin(θ) sin(φ) + χyz B0 cos(θ)
< Mz > = χzx B0 sin(θ) cos(φ) + χzy B0 sin(θ) sin(φ) + χzz B0 cos(θ)

Comparing these values to the components we found for < M > above reveals the surviving components
of the susceptibility tensor and their values:
−2 ~ω0 γ
χxx = χxy = (31)
3 B0 a
We can plug in B0 = − ωγ0 and express χij in tensor form:
 
21 0 0
2 ~γ 
χij = 0 1 0  (32)
3 a
0 0 0

Exercise 6, page 1204

Consider a system formed by an electron spin S and two nuclear spins I1 and I2 (S is, for example, the
spin of the unpaired electron of a paramagnetic diatomic molecule, and I1 and I2 are the spins of the two
nuclei of this molecule).
Assume that S, I1 , and I2 are all spin 21 ’s. The state space of the three-spin system is spanned by the eight

6
orthonormal kets |εs , ε1 , ε2 >, common eigenvectors of Sz , I1z , I2z , with respective eigenvalues εs ~2 , ε1 ~2 , ε2 ~2
(with εs = ±, ε1 = ±, ε2 = ±). For example, the ket |+, −, + > corresponds to the eigenvalues + ~2 for Sz ,
− ~2 for I1z , and + ~2 for I2z .
a. We begin by neglecting any coupling of the three spins. We assume, however, that they are placed in a
uniform magnetic field B parallel to Oz Since the gyromagnetic ratios of I1 and I2 are equal, the Hamiltonian
H0 of the system can be written:
H0 = ΩSz + ωI1z + ωI2z
where Ω and ω are real, positive constants, proportional to |B|. Assume Ω > 2ω.
What are the possible energies of the three-spin system and their degrees of degeneracy?
The eight possible kets of the three-spin system with their associated energies are below:
Ω~
Ĥ0 | + ++ > = + ω~
2
Ω~
Ĥ0 | + +− > =
2
Ω~
Ĥ0 | + −+ > =
2
Ω~
Ĥ0 | + −− > = − ω~
2
Ω~
Ĥ0 | − ++ > = − + ω~
2
Ω~
Ĥ0 | − +− > = −
2
Ω~
Ĥ0 | − −+ > = −
2
Ω~
Ĥ0 | − −− > = − − ω~
2

Both energy values Ω~ Ω~

2 and − 2 are second degree degenerate.
b. We now take coupling of the spins into account by adding the Hamiltonian:

W = aS · I1 + aS · I2

where a is a real, positive constant (the direct coupling of I1 and I2 is negligible).

What conditions must be satisfied by εs , ε1 , ε2 , ε0s , ε01 , ε02 for aS·I1 to have a non-zero matrix element between
|εs , ε1 , ε2 > and |ε0s , ε01 , ε02 >? Same question for aS · I2 .

The first piece of the Hamiltonian W1 = aS · I1 can be expanded as:

W1 = a(Sx I1x + Sy I1y + Sz I1z ) (33)

The matrix element would then be written as:

< ε0s , ε01 , ε02 |a(Sx I1x + Sy I1y + Sz I1z )|εs , ε1 , ε2 >

Since this portion of W doesn’t act on the ket of the second nuclear spin |ε2 >, it can be pulled out, along
with the constant a:

< ε0s , ε01 , ε02 |W |εs , ε1 , ε2 >= a < ε02 |ε2 > [(< ε0s , ε01 |Sx I1x |εs , ε1 >)
+(< ε0s , ε01 |Sy I1y |εs , ε1 >)
+(< ε0s , ε01 |Sz I1z |εs , ε1 >)]

We can analyze each component individually. For the x-component, we need to express Sx and Ix1 in terms
of the raising and lowering operators:
1
Sx = (S+ + S− )
2

7
The matrix element of the x-component of W1 is then:
a < ε02 |ε2 >< ε0s , ε01 |Sx I1x |εs , ε1 >= a < ε02 |ε2 >< ε0s |Sx |εs >< ε01 |I1x |ε1 >
a
= < ε02 |ε2 > [< ε0s |S+ |εs > + < ε0s |S− |εs >]
4
×[< ε01 |S+ |ε1 > + < ε01 |S− |ε1 >]

This matrix element will only be nonzero if ε02 = ε2 , ε01 6= ε1 , and ε0s 6= εs .
The same procedure can be followed for the matrix element of the y-component of W1 , expressing Sy and
Iy1 in terms of the raising and lowering operators:
1
Sy =(S+ − S− )
2i
The matrix element of the y-component of W1 is then:
a
− < ε02 |ε2 > [< ε0s |S+ |εs > − < ε0s |S− |εs >][< ε01 |I1+ |ε1 > − < ε01 |I1− |ε1 >]
4

Again, this matrix element will only be nonzero if ε02 = ε2 , ε01 6= ε1 , and ε0s 6= εs .
The z-component of W1 is simply:
a
< ε02 |ε2 >< ε0s |Sz |εs >< ε01 |I1z |ε1 > (34)
4
The matrix element of the z-component of W1 will be nonzero if ε02 = ε2 , ε01 = ε1 , and ε0s = εs .
Since the total matrix element of W1 is the sum of each component, it will produce a nonzero result as long
as ε02 = ε2 . The same analysis can be carried out for the second term W2 = aS · I2 . In this case, there will
be a nonzero matrix element as long as ε01 = ε1 .
c. Assume that:
a~2  ~Ω, ~ω
so that W can be treated like a perturbation with respect to H0 . To first order in W , what are the eigenvalues
of the total Hamiltonian H = H0 + W ? To zeroeth order in W, what are the eigenstates of H?
We can use the following expression from perturbation theory:
En = En(1) + < φn |Ŵ |φn >
and Eq. 33, along with a similar one corresponding to W2 , to calculate the eigenvalues of the total Hamil-
tonian:

Ω~ Ω~ a~2
E+++ = + ω~+ < + + +|aS · I1 + aS · I2 | + ++ >= + ω~ +
2 2 2
Ω~ Ω~
E++− = + < + + −|aS · I1 + aS · I2 | + +− >= + a~2
2 2
Ω~ Ω~ a~2
E+−+ = + < + − +|aS · I1 + aS · I2 | + −+ >= −
2 2 2
Ω~ Ω~ a~2
E+−− = − ω~+ < + − −|aS · I1 + aS · I2 | + −− >= − ω~ −
2 2 2
−Ω~ Ω~ a~2
E−++ = + ω~+ < + − −|aS · I1 + aS · I2 | + −− >= − + ω~ −
2 2 2
−Ω~ Ω~
E−+− = + < − + −|aS · I1 + aS · I2 | − +− >= −
2 2
−Ω~ Ω~
E−−+ = + < − − +|aS · I1 + aS · I2 | − −+ >= −
2 2
−Ω~ Ω~ a~2
E−−− = − ω~+ < − − −|aS · I1 + aS · I2 | − −− >= − − ω~ +
2 2 2

8
d. Using the approximation of the preceding question, determine the Bohr frequencies which can appear in
the evolution of < Sx > when the coupling W of the spins is taken into account.
We can write the initial state in the basis of eigenstates H, S 2 , Sz , I12 , I1z , I22 , I2z as:

|ψ(0) >= a(0)| + ++ > +b(0)| + +− > +c(0)| + −+ > +d(0)| + −− >
+e(0)| − ++ > +f (0)| − +− > +g(0)| − −+ > +h(0)| − −− >

Its time evolution can be written as:

iE+++ t iE++− t iE+−+ t iE+−− t
|ψ(t) >= a(0)e ~ | + ++ > +b(0)e ~ | + +− > +c(0)e ~ | + −+ > +d(0)e ~ | + −− >
iE−++ t iE−+− t iE−−+ t iE−−− t
+e(0)e ~ | − ++ > +f (0)e ~ | − +− > +g(0)e ~ | − −+ > +h(0)e ~ | − −− >

iE+++ t
where the energies are given in the preceding section. Let a(0)e ~ = a(t) and similarly for the other
terms. The corresponding bra is then:

< ψ(t)| = a(t)∗ < + + +| + b(t)∗ < + + −| + c(t)∗ < + − +| + d(t)∗ < + − −|
+e(t)∗ < − + +| + f (t)∗ < − + −| + g(t)∗ < − − +| + h(t)∗ < − − −|

We want to calculate the evolution of < Sx >:

1 1 1
< ψ(t)|Sx |ψ(t) >=< ψ(t)| (S+ + S− )|ψ(t) >= < ψ(t)|S+ |ψ(t) > + < ψ(t)|S− |ψ(t) >
2 2 2

First, we can look at the action of S+ on the |ψ(t) > ket, which only acts on ms states. Knowing that
S+ |+ >= 0 and S+ |− >= ~|+ >, the first four terms of S+ |ψ(t) > will vanish:
1 1
< ψ(t)|S+ |ψ(t) >= ((a(t)∗ < + + +| + b(t)∗ < + + −| + c(t)∗ < + − +| + d(t)∗ < + − −|
2 2
+e(t)∗ < − + +| + f (t)∗ < − + −| + g(t)∗ < − − +| + h(t)∗ < − − −|)
×(e(t)~| + ++ > +f (t)~| + +− > +g(t)~| + −+ > +h(t)~| + −− >))
1
= (a(t)∗ < + + +|e(t)~| + ++ > +b(t)∗ < + + −|f (t)~| + +− >
2
+c(t)∗ < + − +|g(t)~| + −+ > +d(t)∗ < + − −|h(t)~| + −− >)
~
= (a(t)∗ e(t) + b(t)∗ f (t) + c(t)∗ g(t) + d(t)∗ h(t))
2

Now, we can look at the action of S− on the |ψ(t) > ket. Knowing that S− |− >= 0 and S− |+ >= ~|− >,
the last four terms of S− |ψ(t) > will vanish:
1 1
< ψ(t)|S− |ψ(t) >= ((a(t)∗ < + + +| + b(t)∗ < + + −| + c(t)∗ < + − +| + d(t)∗ < + − −|
2 2
+e(t)∗ < − + +| + f (t)∗ < − + −| + g(t)∗ < − − +| + h(t)∗ < − − −|)
×(a(t)~| − ++ > +b(t)~| − +− > +c(t)~| − −+ > +d(t)~| − −− >))
1
= (e(t)∗ < − + +|a(t)~| − ++ > +f (t)∗ < − + −|b(t)~| − +− >
2
+g(t)∗ < − − +|c(t)~| − −+ > +h(t)∗ < − − −|d(t)~| − −− >
~
= (e(t)∗ a(t) + f (t) ∗ b(t) + g(t)∗ c(t) + h(t)∗ d(t))
2

Adding 21 < ψ(t)|S+ |ψ(t) > + 21 < ψ(t)|S− |ψ(t) > together, we can see that both Ω and ω Bohr frequencies
appear in the evolution of < Sx >.

9
e. Now assume that the magnetic field B is zero, so that Ω = ω = 0. The Hamiltonian then reduces to W .
α. Let I = I1 + I2 be the total nuclear spin. What are the eigenvalues of I2 and their degrees of degeneracy?
Show that W has no matrix elements between eigenstates of I2 of different eigenvalues.
Since I1 = I2 = 21 , the possible values of I are:
|I1 − I2 | < I < I1 + I2 ⇒ 0 < I < 1
Therefore I = 0 or 1. The eigenvalues of I2 are I(I + 1)~2 yielding values of 2~2 or 0.
β. Let J = S + I be the total spin. What are the eigenvalues of J2 and their degrees of degeneracy? Deter-
mine the energy eigenvalues of the three-spin system and their degrees of degeneracy. Does the set {J2 , Jz }
form a C.S.C.O? Same question for {I2 , J2 , Jz }.
1 3
|I − S| < J < I + S ⇒ <J <
2 2
The eigenvalues of J2 are J(J + 1)~2 where J = 21 or 32 . Therefore the possible eigenvalues of J2 are 15 2
4 ~
and 43 ~2 .
To find the energy eigenvalues of the three-spin system in our new basis, we can express Ŵ as:
1
aS · I1 + aS · I2 = aS · (I1 + I2 ) = a(S · I) = a (J2 − I2 − S2 )
2
The eigenvalues are found from Ŵ acting on our new basis |IJMJ >:
a~2
Ŵ |IJMJ >= (J(J + 1) − I(I + 1) − S(S + 1))|IJMJ >
2
MJ ranges from −J to J. The possible states and corresponding energies are therefore:
1 1
Ŵ |0 >=0
2 2
1 1
Ŵ |0 − >=0
2 2
3 3 a~2
Ŵ |1 >=
2 2 2
3 1 a~2
Ŵ |1 >=
2 2 2
3 1 a~2
Ŵ |1 − >=
2 2 2
3 3 a~2
Ŵ |1 − >=
2 2 2
1 1
Ŵ |1 > = −a~2
2 2
1 1
Ŵ |1 − > = −a~2
2 2

a~2
Eigenvalue 0 is twofold degenerate, eigenvalue 2 is fourfold degenerate, and eigenvalue −a~2 is twofold
degenerate.

Exercise 9, page 1207

We want to calculate the ground state energy of the hydrogen atom by the variational method, choosing
as trial functions the spherically symmetrical functions ϕα (r) whose r-dependence is given by:

 r
ϕα (r) = C 1− for r6α
α
ϕα (r) = 0 for r>α

10
C is a normalization constant and α is the variational parameter. a. Calculate the mean value of the kinetic
and potential energies of the electron in the state |ϕα >. Express the mean value of the kinetic energy in
terms of ∇ϕα so as to avoid the ”delta functions” which appear in ∇ϕα (since ∇ϕα is discontinuous).

~2 2
< KE > = < ϕα (r)| − ∇ |ϕα (r) >
2m
2π πZ α
~2
Z Z
r 2 r 2
= −|C|2 1− ∇ 1− r sin(θ)drdθdφ
2m 0 0 0 α α
r 
~2 2π π α  2 d(1 − α )
Z Z Z 
r 1 d
= −|C|2 1− 2 dr
r r2 sin(θ)drdθdφ
2m 0 0 0 α r dr
2 Z 2π Z π Z α 
 
2 ~ r d 1
= −|C| 1− − sin(θ)drdθdφ
2m 0 0 0 α dr α
~2 2π π α 
Z Z Z  
r 2r
= −|C|2 1− − sin(θ)drdθdφ
2m 0 0 0 α α
Z α
~2
 
r 2r
= −|C|2 4π 1− − dr
2m 0 α α
2π~2 α
= |C|2
3m
Solving for the normalization constant C:

< ϕα |ϕα > = 1

Z 2π Z π Z α  r 2 2
= |C|2 1− r sin(θ)drdθdφ
0 0 0 α
Z α  r 2 2
= |C|2 4π 1− r dr
0 α
α3
= |C|2 2π
15

Solving for |C|2 yields:

15
|C|2 =
2πα3
Plugging in the value for C in the above expression for < KE > yields:

15 2π~2 α
< KE > =
2πα3 3m
5~2
=
mα2
The expectation value of the potential energy is found using the Coulomb potential:

e2
< PE > = < ϕα (r)| − |ϕα (r) >
4π0 r
Z 2π Z π Z α   2 
r e
= −|C|2 1− r2 sin(θ)drdθdφ
0 0 0 α 4π 0 r
Z 2π Z π Z α   2 
2 r 2 e
= −|C| 1− r2 sin(θ)drdθdφ
0 0 0 α 4π 0 r
2Z α 2
e r
= −|C|2 1− rdr
0 0 α
e2 α 2
 
= −|C|2
0 12

11
Plugging in the value for C yields:

5e2
< P E >= − (35)
8πα0
b. Find the optimal value α0 of α. Compare α0 with the Bohr radius a0 . Use the variational method:

< ϕα (r)|Ĥ|ϕα (r) > = < ϕα (r)|KE + P E|ϕα (r) >

= < KE > + < P E >
5~2 −5e2
= 2
+
mα 8πα0
= E(α)

Find the derivative of E(α) with respect to α and set it to zero to find optimal value α0 :

dE(α) 10~2 5e2

= − + =0
dα mα3 8π0 α2
10~2 5e2
=
mα3 8π0 α2

Solve for α which serves as optimal value of α0 :

16~2 π0
α0 = (36)
me2
Comparing this value to the Bohr radius:
4π0 ~2
a0 = (37)
me2
Produces:
α0 = 4a0
c. Compare the approximate value obtained for the ground state energy of the exact value −EI
The exact value of the ground state energy can be expressed in terms of a0 :

e2 me4
−EI = =
8π0 a0 32π 2 20 ~2

Plugging in α0 into our expression for E gives us the approximate value for the ground state:

5~2 5e2
E(α0 ) = 2 −
mα0 8πα0 0
2
2
me2 5e2 me2

5~
= −
m 16~2 π0 8π0 16~2 π0
4
me4
 
5me 5
= − = −
256π 2 20 ~2 32π 2 20 ~2 8
 
5
= − EI
8

12