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Exercises for Quantum Mechanics

(TFFY54)

Johan Henriksson and Patrick Norman

Department of Physics, Chemistry and Biology,


Linköping University, SE-581 83 Linköping, Sweden

Spring Term 2007


1
For a Hermitian operator Ω̂, we know that
Z Z  ∗
ψ ∗ Ω̂ψ dr = Ω̂ψ ψ dr, ∀ψ.

Show that Z Z  ∗
ψ1∗ Ω̂ψ2 dr = Ω̂ψ1 ψ2 dr, ∀ψ1 , ψ2 .
Hint: Consider a linear combination Ψ = c1 ψ1 + c2 ψ2 , where c1 , c2 ∈ C.

2
Consider a one-dimensional harmonic oscillator with mass m and characteristic
frequency ω. At time t = 0, the state is given by
1
Ψ(x) = √ (ψ0 (x) + ψ1 (x)),
2
where ψn (x) are eigenstates to the Hamiltonian with energies En = ~ω(n+1/2).
Determine the time-dependent state vector Ψ(x, t) for t > 0.

3
Let ψ(x) be a solution to the time-independent Schrödinger equation with a
potential V (x) that is symmetric with respect to the origin, i.e., V (−x) = V (x).
a) Show that ψ(−x) also is a solution with the same energy eigenvalue.
b) If the energy levels are nondegenerate (i.e., there is at most one eigen-
function associated with a given energy), show that ψ(−x) = ψ(x) or
ψ(−x) = −ψ(x), i.e., the eigenfunctions are either symmetric or antisym-
metric with respect to the origin.

4
A particle (mass m) is incident from the left towards the potential step
(
0 x≤0
V (x) =
V0 x > 0
The energy of the particle is E = 2V0 , V0 > 0.
a) Solve the time-independent Schrödinger equation.
Note: Since the particle is unbounded it is not possible to normalize the
wave function.
b) Calculate the probability current density j.
c) Define and calculate the transmission T using the result in b).
d) Define and calculate the reflection R using the result in b).
e) Calculate R and T and check that R + T = 1.

1
5
Show that the expectation value of the momentum operator hp̂i is real for the
wave packet
Z∞
1
ψ(x) = √ eixp/~ Φ(p) dp.
2π~
−∞

6
Determine the wave function in x-space corresponding to

a) (
(2ξ)−1/2 |k| ≤ ξ
ϕ(k) =
0 otherwise

b)
k2
 
1
ϕ(k) = √ exp − 2
2πσ 2σ

7
Consider the time-dependent Schrödinger equation

i~ ψ(r, t) = Ĥψ(r, t).
∂t
If the potential is time-independent, i.e., V (r) 6= V (r, t), show that it is possible
to find solutions separable in space and time, i.e., ψ(r, t) = ψ(r)f (t). Find the
explicit form of f (t) and show that ψ(r) is a solution of an eigenvalue problem.

8
A particle of mass m in a one-dimensional box
(
0 0≤x≤a
V (x) =
∞ otherwise

is in a mixed state composed of the ground state and the first excited state. The
normalized wave function can be written as

Ψ(x) = c1 ψ1 (x) + c2 ψ2 (x),

where c1 and c2 are constants and ψ1 (x) and ψ2 (x) are eigenfunctions cor-
responding to the ground state and the first excited state, respectively. The
2 2
average value of the energy is πma~2 . What can be said about c1 and c2 ?

2
9
If hψ|Ω̂|ψi is real for all ψ, show that

hψ1 |Ω̂|ψ2 i = hψ2 |Ω̂|ψ1 i∗

for all ψ1 and ψ2 . N.b., solve the problem without assuming that Ω̂ is Hermitian.
Hint: Consider the linear combinations Ψ = ψ1 + ψ2 and Ψ = ψ1 + iψ2 , respec-
tively.

10
Let {ψn } be a complete set of orthonormal functions which are solutions to the
time-independent Schrödinger equation Ĥψn = En ψn . At t = 0 the system is
described by the wave function
1 1 1
Ψ(x) = √ eiα ψ1 (x) + √ eiβ ψ2 (x) + √ eiγ ψ3 (x).
2 3 6
a) Write down Ψ(x, t).
b) At time t a measurement of the energy of the system is performed. What
is the probability to obtain the result E2 ?
c) Calculate hĤi
d) Is the mean value of the energy equal to any of the possible outcomes of
a measurement?

11
A particle of mass m is moving in the one-dimensional potential
(
0 0≤x≤a
V (x) = .
∞ otherwise

At a certain time the particle is in a state given by the wave function

Ψ(x) = N x(a − x)

where N is a normalization constant.

a) Calculate the probability that a measurement of the energy yields the


ground state energy.
b) Calculate the probability that a measurement of the energy yields a result
2 2
between 0 and 3~ π
ma2 .

3
12
Consider a particle (mass m) in a one-dimensional box (0 ≤ x ≤ a). At time
t = 0, the particle is described by the wave function
"r #
2 π  r2 

Ψ(x) = N sin x + sin x .
a a a a

a) Determine N and Ψ(x, t).


b) Calculate hxit = hΨ(x, t)|x̂|Ψ(x, t)i.

Hint: sin(ϕ) · sin(4ϕ) = [cos(3ϕ) − cos(5ϕ)]/2

13
Verify the following relations for matrix exponentials.

a) exp(A)† = exp(A† )
b) B exp(A)B−1 = exp(BAB−1 )
c) exp(A + B) = exp(A) exp(B) if [A, B] = 0
d) exp(−A) exp(A) = 1
d
e) dλ exp(λA) = A exp(λA) = exp(λA)A, A 6= A(λ)
f) exp(−A)B exp(A) = B + [B, A] + 12 [[B, A], A] + 1
3! [[[B, A], A], A] + ...
Hint: Consider the Taylor expansion of exp(−λA)B exp(λA) around λ = 0.

14
Define the trace of an operator as
X X
Tr(Ω̂) = hi|Ω̂|ii = Ωii
i i

and the density operator, commonly used in many applications, as ρ̂ = |ψihψ|.


a) Show that Tr(Ω̂Λ̂) = Tr(Λ̂Ω̂).
b) If the basis |ii is transformed by a unitary transformation, i.e., |i′ i = Û|ii,
show that the trace of the operator is unchanged in the new basis.
c) Show that Tr(ρ̂) = 1.
d) Show that it is possible to use ρ̂ to express the expectation value of an
operator as hΩ̂i = Tr(ρ̂Ω̂).
Comment: This means that expectation values of observables are not affected
by the choice of representation (basis) we make for our wave functions since the
trace is invariant under unitary transformations.

4
15
In a three-dimensional vector space, assume that we have found the commuting
operators Ω̂ and Λ̂ corresponding to some physical observables. We choose a
basis |ni, n = {1, 2, 3}, for which none of the operators are diagonal but given
by the matrix representations
   √ 
2 0 i 3
√ −i 2 √i
1
Ω =  0 1 0 and Λ = i 2 √2 2 .
2
−i 0 2 −i 2 3

a) Solve the eigenvalue problem Ω̂|ωi = ω|ωi to find which values of the
observable Ω we can measure.
b) Since one eigenvalue is degenerated, the eigenstates are not uniquely de-
fined through the eigenvalues ω. To resolve this problem, we can use the
commuting operator Λ̂. Show that Λ is block diagonal in the basis |ωi.
c) Diagonalize the 2 × 2 block in Λ to find a basis in which both Ω and Λ
are diagonal.
d) The pairs of eigenvalues |ω, λi uniquely defines the eigenstates. Which are
the three pairs of eigenstates?
Comment: This exercise is closely related to real problems such as the hydrogen
atom where one of the observables usually is the Hamiltonian and you encounter
degenerate energy levels.

16
Consider a Hermitian operator Ω̂.

a) Show that exp(iΩ̂) is unitary.


b) Given the result in a), show that a wave function normalized at t = t0 will
remain normalized at any t > t0 .
c) Show that nondegenerate eigenstates of Ω̂ are orthogonal.
d) Show that eigenvalues and expectation values of Ω̂ are real.

17
In a three-dimensional vector space the operator Ω̂ can be represented as
 
2 0 i
Ω=0 1 0 .
−i 0 2
p
Find the matrix representation of the operator Ω̂, i.e., the operator which
when squared yields the operator Ω̂.

5
18
Let Û(a) be a unitary operator defined as

Û(a) = e−iap̂/~ ,

where a is a real number of dimension length. Furthermore, define the transfor-


mation of an arbitrary operator Ω̂ as

Ω̃ = Û † (a)Ω̂Û (a).

a) What does this transformation correspond to in your laboratory?


Note: The wave function will be left unchanged in this case.
b) Determine the transformed coordinate and momentum operators x̃ and p̃.
c) If you got the correct answers in b), it is trivial to determine the expecta-
tion values hx̃i and hp̃i. These averages should reflect your answer in a).
Determine these expectation values.

d) If we, instead of transforming the operators, transform our state vectors


according to
|ψ̃i = Û(a)|ψi,
what does |ψ̃i correspond to in your laboratory? Note that the observ-
ables, of course, will be unaltered, i.e., hψ̃|Ω|ψ̃i = hψ|Ω̃|ψi.

19
A harmonic oscillator of mass m is in a state described by the wave function
1 i 1 i
Ψ(x, t) = √ eiβ ψ0 (x)e− ~ E0 t + √ e−iβ ψ1 (x)e− ~ E1 t ,
2 2
where β is a real constant, ψ0 and ψ1 are the ground and the first excited
states, respectively, and E0 and E1 are the corresponding energies. Determine
the expectation values of Ĥ and x̂.

20
Consider a harmonic oscillator of mass m with eigenstates |ψn i and energy levels
En = ~ω(n + 21 ). The Hamiltonian for this system is Ĥ = p̂2 /2m + mω 2 x̂2 /2.
For this system, show that
* +
∂En ∂ Ĥ
= ψn ψn .

∂ω ∂ω

Comment: This is a direct result of the much more general Hellman–Feynman


theorem in quantum mechanics.

6
21
A particle of mass m is located in the potential V (x) = mω 2 x2 /2 . The particle
is not in a stationary state and is at time t = 0 described by the wave function

X
|Ψ(0)i = cn |ni.
n=0

We can assume that the wave function is real at t = 0, i.e., all cn are real
numbers. Show that the time-dependent average value of the position hx̂it is

hx̂it = hx̂it=0 cos ωt.

Comment: The average of the position is oscillating with a frequency ω (much


like a classical particle). The frequency ω is related to the energy in the usual
way, i.e., En = ~ω(n + 1/2).

22
Consider a one-dimensional harmonic oscillator (mass m) in state ψn .
a) Show that the uncertainty product in this state is given by
 
1
(∆x)n (∆p)n = n + ~, n = 0, 1, 2, . . .
2

b) What is so special with the case n = 0?


c) Show that
1 1
hT̂ in = hV̂ in = En = hĤin .
2 2

23
Consider a harmonic oscillator in the energy basis {|ni}, with Ĥ|ni = En |ni
and En = ~ω(n + 1/2). In order to make a transition from energy basis to a
representation in ordinary space, ψn (x), we can exploit the properties of the
creation and annihilation operators, ↠|0i = |1i and â|1i = |0i, where
   
1 d 1 d
↠= √ ξ− and â = √ ξ+ .
2 dξ 2 dξ

Determine ψ0 (ξ) and ψ1 (ξ).

24
A particle in a system with V (x) = V (−x) is described by the wave function
σ 2 x2
Ψ(x) = σ 1/2 π −1/4 e− 2 .

7
If Ψ(x) is expanded in eigenfunctions to the Hamiltonian,

X
Ψ(x) = cn ψn (x),
n=0

half of the coefficients can be determined using a simple symmetry argument.


How?

25
A particle is moving in a central potential, V (r), corresponding to a potential
function approaching zero as the distance r to the center approaches infinity.
The particle is in a stationary state where the time-independent part of the
wave function is given by
Ψ(x, y, z) = N xye−αr ,
where N is a normalization constant and α is a given positive constant.
a) Calculate the possible results when measuring L̂2 and L̂z and state the
corresponding probabilities.
b) Determine the potential V (r).

26
A hydrogen atom is in the 2p state with ml = 0 and ms = 1/2. The system is
thus represented by the wave function
 
1 −iE2 t/~
ψ2,1,0, 21 (r, θ, φ, t) = R2,1 (r)Y1,0 (θ, φ) e .
0
At time t = 0, a measurement of the orbital angular momentum along the x-axis
is performed.
a) Motivate why the magnitude of the orbital angular momentum remains
unchanged by the measurement, i.e., the state at time t > 0 will still be
an eigenstate of L̂2 with eigenvalue l = 1.
b) Determine the possible values and corresponding probabilities in the mea-
surement performed at time t = 0.

27
a) For a centrosymmetric system with V = V (r), show that
[L̂z , V̂ ] = 0 and [L̂z , p̂2 ] = 0.

p̂2
b) Show furthermore that if Ĥ = 2m + V̂ , it follows that

[L̂z , Ĥ] = 0 and [L̂2 , Ĥ] = 0.

c) What consequences do these results have?

8
28
For a system with l = 1, determine the matrix representation of L̂2x .

29
Study a state |ψi given by hr, θ, φ|ψi = ψ(r, θ, φ) in coordinate basis. In this
basis, determine the transformed state e−iφ0 L̂z /~ |ψi.
Hint: The effect of L̂z in the coordinate basis is −i~∂/∂φ.

30
Consider ψ(r, θ, φ) = f (r) Yl,m (θ, φ), where Yl,m (θ, φ) is a spherical harmonic.
We want to make a simultaneous measurement of Lx and Ly , but an uncertainty
in the measurement is unavoidable.
a) Why?
b) For a given (fixed) value of the quantum number l, find the value of m
which leads to the largest possible accuracy if Lx and Ly are measured
simultaneously.
2 2
Hint: Minimize D(m) = (∆Lx ) + (∆Ly )
c) What is the smallest possible accuracy if Lx , and Ly is measured simul-
taneously?
d) What happens in the special case of l = 0?

31
Consider a particle of mass m moving in the potential
(
0 0≤x≤a
V (x) = .
∞ otherwise
In nonrelativistic quantum mechanics (i.e., v ≪ c) the energy levels, as we all
know, are determined by
n2 π 2 ~2
En = , n = 1, 2, 3, . . .
2ma2
and the corresponding normalized wave functions are given by
(q
2
sin nπx

a a 0≤x≤a
ψn (x) =
0 otherwise.
We want to make an approximation of the relativistic correction to the energy
En using perturbation theory. For the kinetic energy we have (according to the
theory of relativity)
"r #
p  p 2
2 2 2 2 2
Ek = (pc) + (mc ) − mc = mc 1+ −1
mc

9
If this is expanded for small linear momenta this yields
p2 p4
Ek = − + ...,
2m 8m3 c2
4
p2
which gives us a correction − 8mp3 c2 to the nonrelativistic expression 2m for the
kinetic energy.
a) What is, quantum mechanically, the perturbative part of the Hamiltonian?
b) Use this Hamiltonian to make a first -order perturbation theory calculation
(0)
of the relativistic correction to the unperturbed energy level En and
(0)
compare quantitatively the correction term with En .

32
In a hydrogen atom, the electrostatic interaction between the electron and the
proton in the nucleus results in the potential energy given by (in spherical co-
ordinates)
e2 1
V (r, θ, φ) = V (r) = − .
4πǫ0 r
The time-independent Schrödinger equation is separable, Ψ(r, θ, φ) = ψn (r) Yl,m (θ, φ),
where Yl,m (θ, φ) are spherical harmonics. In spherical coordinates, the Hamil-
tonian is given by
~2 1 d2 e2 L̂2
Ĥ = − r − + ,
2µ r dr2 (4πǫ0 )r 2I
where µ is the reduced mass of the electron and the proton, I is the moment of
inertia, and L̂ is the angular momentum operator.
a) Use the variational principle to estimate the ground state energy for the
electron in a hydrogen atom.
Hint: Due to the fact that the potential energy does not depend on the
angles θ and φ, a suitable trial function for the ground state is φ = φ(r) =
N exp(−αr), where α ≥ 0 is the variational parameter.
b) How good/bad is the estimate? Why so?

33
Consider a particle with mass m moving in the two-dimensional potential
(
0 0 ≤ x ≤ a and 0 ≤ y ≤ a
V (x, y) = .
∞ otherwise

Using first-order perturbation theory, show that the degeneracy of the first ex-
cited state is lifted by the perturbation
Ĥ ′ = ǫx̂2 ,
where ǫ is small. Visualize the energy levels schematically in a graph. Which
are the proper zeroth-order eigenfunctions?

10
34
A hydrogen atom in state |1, 1, 0, + 21 i is subjected to a time-dependent mag-
netic field, B(r, t) = B0 ex sin(ωt). Neglecting terms quadratic in the magnetic
field, the interaction between the electron and the external magnetic field, B, is
described by the Hamiltonian
µB
Ĥ ′ = (L̂ + 2Ŝ) · B,
~
where µB is the Bohr magneton. Determine the possible final states. Comment
on these final states in comparison with those of an perturbing electric field?

35
Using the variational principle, estimate the ground state energy for a one-
dimensional anharmonic oscillator with potential V (x) = λx4 . Make the as-
sumption s
β 2 2
φ(x) = √ e−β x /2 , hφ|φi = 1.
π

36
A one-dimensional harmonic oscillator (mass m, force −mω 2 xex ) is perturbed
by a small force −mǫxex where 0 < ǫ ≪ ω. Using perturbation theory, deter-
mine the corrections to the unperturbed energy levels to second order. Further-
more calculate the exact energy levels of the perturbed system and compare the
results.

37
A particle with spin 21 is in the state |αi = 10 . If the spin is measured along


the en -direction forming an angle θ with the z-axis, what are the probabilities
of getting the results + ~2 and − ~2 , respectively?

38
Consider a particle of spin s = 1/2 in a time-dependent magnetic field B =
B cos(ωt)ez . The Hamiltonian becomes Ĥ = µB B σ̂z cos(ωt). Assume that the
spin state at time t = 0 is |χ(0)i = |βx i.
a) Calculate |χ(t)i.
b) Calculate hχ(t)|Ŝx |χ(t)i.

11
39
In spin space it is possible to describe an infinitesimal rotation δα around the
y-axis by the unitary operator
i
Û (δα ey ) = Iˆ − δα Ŝy .
~

a) Show that Û (αey ) = exp(−iασ̂y /2).

b) Let Û (αey ) operate on an arbitrary state χ and show that this is equivalent
to a rotation of the spin vector by an angle α/2 in spin space.
c) What is the expected result of a rotation by the angle 2π? Make a 2π
rotation, and compare to the expected result. How many turns must a
spin vector be rotated in order to get back to its original state?

40
In magnetic resonance, the magnetic moment, m, of a particle interacts with
the applied magnetic field. This interaction is described by the Hamiltonian

Ĥ = −m̂ · B,

where the components of the magnetic dipole moment operator are m̂i = −µB σ̂i
and µB is the Bohr magneton. Assume that a constant magnetic field B = Bez
is applied. At time t = 0, the spin is measured to be +~/2 in the x-direction,
i.e., |χ(0)i = |αx i.
a) Calculate |χ(t)i by using the propagator

|χ(t)i = e−iĤt/~ |χ(0)i.

b) Calculate |χ(t)i by solving the time-dependent Schrödinger equation using


the assumption  
a(t)
|χ(t)i = .
b(t)

c) Let t > 0. Calculate the probability to obtain the result −~/2 in a mea-
surement of the spin along the x-direction.
d) Let t > 0. Calculate the probability to obtain the result +~/2 in a mea-
surement of the spin along the z-direction.

41
Determine the eigenvalues of the operator en · Ŝ, where en = (sin θ, 0, cos θ) and
Ŝ is the spin operator for a particle with spin 12 . The eigenvalues correspond to
the possible measured values when measuring spin along the direction en .

12
42
Consider the spin operators
     
~ 0 1 ~ 0 −i ~ 1 0
Ŝx = , Ŝy = , Ŝz = .
2 1 0 2 i 0 2 0 −1
~2 ˆ
a) Show that Ŝx2 = Ŝy2 = Ŝz2 = 4 I.

b) Determine the eigenvalues and eigenvectors to Ŝx and Ŝy .

c) Show the anticommutation relation [Ŝx , Ŝy ]+ = Ŝx Ŝy + Ŝy Ŝx = 0.

43
The spin and angular dependent part of the wave function for an electron is
given by:
r r
2l 1
Φ(θ, φ) = Yl,l−1 (θ, φ)|αi + Yl,l (θ, φ)|βi
2l + 1 2l + 1
where Yl,m (θ, φ) are normalized spherical harmonics (eigenfunctions to L̂2 and
L̂z ) and    
1 0
|αi = and |βi =
0 1
are eigenstates to Ŝ 2 and Ŝz .
Show that Φ(θ, φ) is an eigenfunction to the z-component of the angular
momentum operator, Jˆz = L̂z + Ŝz , and calculate the corresponding expectation
value.

44
At time t = 0, the spin state of an electron is given by
√ 
1 2
|χ(0)i = .
2 1+i
a) Determine the direction
 
sin θ cos φ
en =  sin θ sin φ 
cos θ
along which to apply a magnetic field, i.e., B = B0 en , such that, at time
t = t0 , the spin state is given by
 
1
|χ(t0 )i = .
0

b) How long time will you need to apply the magnetic field?
Hint: The Hamiltonian of the system is Ĥ = µB B · σ̂, where µB is the
Bohr magneton.

13
45
From the point of view of the electron, the orbital motion of the proton in
hydrogen creates an magnetic field of considerable strength—the numerical value
of the magnetic field experienced by the electron is in the order of 0.4 Tesla.
Due to this strong internal magnetic field, the energy of the atom will depend
on the orientation of the electron spin.
The interaction operator that needs to be added to the nonrelativistic Hamil-
tonian in order to describe spin-orbit interaction is
~α 1
ĤSO = L̂ · Ŝ,
2m2 c r3
where m is the electron mass, c is the speed of light, and α is the dimensionless
fine-structure constant (α ≈ 1/137).
Consider hydrogen in its 2p-state. Without consideration made to the spin-
orbit interaction this state is sixfold energy degenerate.
a) Give a complete set of commuting observables for hydrogen when spin-
orbit interaction is accounted for.
b) Describe qualitatively how the energy degeneration of the six states will
change in this case.
c) Determine numerical values of any energy splittings you have proclaimed
above. Also, give the energy separation between the 1s and 2p levels in
order to make sure that the corrections are small in absolute terms.

46
At time t = t0 a hydrogen atom, described by the wave function
p ! 
x2 + y 2 + z 2 1
ψ(x, y, z, t0 ) = N x exp − ,
2a0 −i

where N is a normalization constant and a0 is the Bohr radius, is placed in


a constant external magnetic field B = B0 ez . The Hamiltonian describing
the interaction with the external field is Ĥ = µB B0 σ̂z . Calculate the time-
dependent expectation values of the spin projection along the x-, y-, and z-axes.

47
At time t0 , the wave function of a hydrogen atom is given by
p ! 
x2 + y 2 + z 2 1
ψ(x, y, z, t0 ) = N x exp − ,
2a0 −i

where N is a normalization constant and a0 is the Bohr radius.


a) If we measure the orbital angular momentum projection along the z-axis,
which values will we measure and what are their respective probabilities?
b) If we measure the projection of the spin along the x-, y, and z-axes, which
values will we measure and what are their respective probabilities?

14
48
a) Using the variational method, show that the virial theorem

2hT̂ i + hV̂ i = 0,

where hT̂ i is the kinetic energy and hV̂ i is the potential energy, is satisfied
for a hydrogen atom.
Hint: Assume that the true normalized wave function is Ψ(x, y, z) and use
as a normalized variational wave function

ψη (x, y, z) = η 3/2 ψ(ηx, ηy, ηz)

where η is a scaling parameter. Here η = 1 corresponds to the exact


solution.
b) For a hydrogen-like system in its ground state, calculate
 
1 1
, , hp̂2x i, hp̂2y i, hp̂2z i, and hp̂2 i.
hr̂i r̂

49
Consider a spinless particle with mass m and charge −e in the potential
(
1
mω 2 x2 , y ∈ [0, a]
V (x, y) = 2
∞, otherwise

where
3π 2 ~
ω= .
2ma2
The system is in the first excited state when a weak electric field is applied
according to E = Een , en = cos θ ex + sin θ ey . To first order, determine the
effect of the perturbing electric field on the energy of the system. Comment on
the θ-dependence of the perturbation.
Hint: Z a  nπx  a2
x sin2 dx =
0 a 4

50
A hydrogen atom is in the 2p state with ml = 0 and ms = 1/2, and the system
is thus represented by the wave function
 
1
ψ2,1,0,1/2 (r, θ, φ) = R2,1 (r)Y1,0 (θ, φ) .
0

Determine the expectation value of the total angular momentum Jˆ2 .

15
51
A complete set of commuting observables for the hydrogen atom is given by
the set of operators Ĥ, L̂2 , L̂z , Ŝ 2 , and Ŝz and the set common eigenkets can
be denoted as |n, l, ml , 1/2, ms i. The 2p-level of the hydrogen atom is sixfold
degenerate due to the different values ml and ms .
Another complete set of commuting observables is given by the set of op-
erators Ĥ, Jˆ2 , Jˆz , L̂2 , and Ŝ 2 and the set common eigenkets can in this case
be denoted as |n, j, mj , l, 1/2i. In terms of the above “old” eigenkets, derive
explicit expressions for the six wave functions that correspond to the 2p-level in
this “new” basis .

52
The spin-orbit interaction operator is given by

ĤSO = A L̂ · Ŝ,

where A is a scalar that is independent of (θ, φ). By re-writing the spin-orbit


operator, motivate why this problems involving this operator should be solved
in the basis |j, mj i that are eigenvectors of Jˆ2 and Jˆz .

53
Assume that the electron in hydrogen is in a d-orbital, i.e., l = 2. If one considers
the interaction between the spin and orbital motion, this level will no longer be
10-fold energy degenerate. The energy operator that describes the interaction
is
ĤSO = A L̂ · Ŝ,
where A is a scalar that is independent of (θ, φ).
a) The possible values of j are l ± 1/2, what are the interaction energies in
these two cases?

b) Express |j, mj i = |5/2, 5/2i in terms of the “old”basis vectors |l, ml , s, ms i.


Show with an explicit calculation that your linear combination of old basis
vectors is an eigenstate of Ĵ2 and Jˆz .

54
Let us consider a hydrogen atom described by the wave function
 √ 
1 2 Y1,0 (θ, φ)
ψ(r) = √ R2,1 (r) .
3 Y1,1 (θ, φ)

a) Is this state an eigenstate to total angular momemtum operators Jˆ2 and


Jˆz , and, if so, what are the values of the corresponding quantum numbers
j and mj ?

16
b) With use of first-order perturbation theory, determine the shift in energy
relative to the 2p-level in hydrogen as due to spin-orbit coupling.
~α 1
Hint: The spin-orbit coupling operator is ĤSO = 2m 2 c r 3 L̂ · Ŝ, where m is the

electron mass, c is the speed of light, and α is the dimensionless fine-structure


constant (α ≈ 1/137). The following integral may be needed hr−3 iR2,1 =
a0−3 /24, where a0 is the Bohr radius.

55
At t = 0 the wave function for the electron in hydrogen is given by
 
1
ψ(x, y, z, 0) = N yze−r/3a0 ,
2i

where N is a normalization constant. Determine the possible values and prob-


abilities in measurements of Jˆz , L̂z and Ŝz .

17
Answers
2.
Ψ(x, t) = √1 (ψ0 (x)e−iωt/2 + ψ1 (x)e−i3ωt/2 )
2

4.
 √ √  √ 
Ai ei(2 mV0 x/~−ωt) + Ar e−i(2 mV0 x/~+ωt) , x ≤ 0 Ar = √2−1 Ai
2+1
a) Ψ(x, t) = √  √ 
At ei( 2mV0 x/~−ωt) 2 2
, x>0 At = √
2+1
Ai

 q √ q
2 V0 (|Ai |2 − |Ar |2 ) = 8 √2 V0 2
m |Ai | , x ≤ 0
b) jx = q m √ q
3+2 2
 2V0 |A |2 = 8 √2 V0 2
m t 3+2 2 m |Ai | , x>0

4 √2
c) T = 3+2 2

3−2√2
d) R = 3+2 2

6.
a) ψ(x, 0) = (πξ)−1/2 sin(ξx)/x
b) ψ(x, 0) = (2π)−1/2 exp(−σ 2 x2 /2)
7.
a) N = 2−1/2  
2 2 2 2
Ψ(x, t) = a−1/2 sin(πx/a)e−iπ ~t/2ma + sin(4πx/a)e−i8π ~t/ma

8.
2
|c1 |2 = 3
1
|c2 |2 = 3

10.
a) Ψ(x, t) = √1 ei(α−E1 t/~) ψ1 + √1 ei(β−E2 t/~) ψ2 + √1 ei(γ−E3 t/~) ψ3
2 3 6

b) P2 = 1/3
E1 E2 E3
c) hĤi = 2 + 3 + 6

d) No
11.
960
P(E1 ) = |c1 |2 = π6

P(E2 ) = |c2 |2 = 0
3~2 π 2 960
P(0 ≤ E ≤ ma2 ) = |c1 |2 + |c2 |2 = π6

18
12.
a) N = 2−1/2     
πx π 2 ~t 4πx 2
Ψ(x, t) = a−1/2 sin exp −i 8π ~t
 
a exp −i 2ma 2 + sin a ma2

a 2a E4 −E1
1 1
 
b) hx̂it = 2 − π2 9 − 25 cos ~ t
15.
a) ω1 = 1 ←→ |ω1 i = 2−1/2 (1, 0, i)T
ω2 = 1 ←→ |ω2 i = (0, 1, 0)T
ω3 = 3 ←→ |ω3 i = 2−1/2 (1, 0, −i)T
 
1 −i 0
b) U† ΩU =  i 1 0
0 0 2

c) |ω1 , λ1 i = 2−1/2 (|ω1 i − i|ω2 i)


|ω2 , λ2 i = 2−1/2 (|ω1 i + i|ω2 i)
|ω3 , λ3 i = |ω3 i
d) |ω, λi = {|1, 0i, |1, 2i, |3, 2i}
17.
 √ √ 
√ 1+ 3 0 ( 3 − 1)i
1 
Ω= 2 0√ 2 0√ 
(1 − 3)i 0 1+ 3
18.
a) The system is fixed, but you are performing measurement w.r.t. to a trans-
lated coordinate system.
b) x̃ = x̂ + a and p̃ = p̂
c) hx̃i = hx̂i + a and hp̃i = hp̂i
d) The system is moved within the laboratory.
19.
E0 +E1
hEi = 12 (E0 + E1 ) = ~ω where ω = 2~ .
 ~
 12
hx̂i = 2mω cos(ωt + 2β)
23.
2
1
ψ0 (ξ) = π 1/4
e−ξ /2
21/2 2
ψ1 (ξ) = π 1/4
ξe−ξ /2
24.
cn = 0 if n is an odd number.

19
25.
a) The only possible measurement result for L̂2 is 6~2 (with probability 1).
Possible results when measuring L̂z are ±2~, each with probability 21 .
2
b) The potential is V (r) = − 3~ α
mr .

26.
a) L̂2 and L̂z are commuting observables.
b) The measured values are ±~, both with probability 1/2.
28.
 
1 0 1
~2
L2x = 2
0 2 0
1 0 1
29.
e−iφ0 L̂z /~ |ψi = ψ(r, θ, φ − φ0 )
30.
a) [L̂x , L̂y ] 6= 0
b) D(m) = l(l + 1)~2 − m2 ~2
c) ~2 l(l + 1)
d) D(m) = 0, i.e., it is possible to determine both L̂x and L̂y simultaneously.
31.
 0

En
b) Enpert = En0 1 − 2mc2

32.
4
a) E0 ≤ − 32πµe
2 ~2 ε2
0

33.
1 1
1 1
ǫa2 and ǫa2 , respectively.
 
The shifts in energy are 3 − 2π 2 3 − 8π 2

34.
(
∆ml = ±1, ∆ml = 0
∆l = 0,
∆ml = 0, ∆ml = −1
35.
 2/3
34/3 ~2
Emin = 4 2m λ1/3

36.
1 ǫ2
Enpert = Enexact = ~ω n +

2 − 2mω 2

20
37.
θ
Pα = cos2 2

Pβ = sin2 θ
2
38.
h     i √
a) |χ(t)i = exp −iµ BB
~ω sin(ωt) |α z i − exp iµB B
~ω sin(ωt) |β z i / 2
 
b) hχ(t)|Ŝx |χ(t)i = − ~2 cos 2µ~ω
BB
sin(ωt)
40.

a) |χ(t)i = [exp(−iµB Bt/~)|αz i + exp(+iµB Bt/~)|βz i] / 2
 
c) Pαx = cos2 µB~Bt
1
d) Pαz = 2
41.
2
λ = ± ~2
42.
√1 1 √1 1
b) Ŝx : + ~2 ↔ and − ~2 ↔
 
2 1 2 −1
.
√1 1 √1 1
Ŝy : + ~2 ↔ and − ~2 ↔

2 i 2 −i
.

43.
hJˆz i = (l − 12 )~
44.
a) en = 2−1/2 (1, −1, 0)T
π~
b) t0 = 4µB B
45.
a) Ĥ, Jˆ2 , Jˆz , L̂2 , and Ŝ 2
(c) ∆E ≈ 4.5 · 10−5 eV
46.
 
~ µB B
hŜx it = 2 sin ~ (t − t0 )
 
µB B
hŜy it = − ~2 cos ~ (t − t0 )

hŜx it = 0

21
47.
a) Measuring Lz yields ±~, both with probability 1/2.
b) Measuring Sx yields ±~/2, both with probability 1/2.
Measuring Sy yields −~/2.
Measuring Sz yields ±~/2, both with probability 1/2.

48.
1 2Z
b) hr̂i= 3a0

1 Z
r̂ = a0
 2
1
hp̂2x i = hp2y i = hp2z i = 3
~Z
a0

49. First excited state is double degenerate with E1 = E2 = 11π 2 ~2 /(4ma2 ).


The first-order energy correction is the same for both states and equals ∆E1 =
∆E2 = 21 aeE sin θ.
50. hJˆ2 i = 11
4 ~
2

51. The |j, mj , l, 1/2i kets take the form


 q 
l±mj +1/2
l,s=1/2 ± 2l+1 Yl,m j −1/2 (θ, φ)
Yj=l±1/2,mj (θ, φ) =  q .
l∓mj +1/2
2l+1 Yl,mj +1/2 (θ, φ)

53. a)
A~2

l; j = l + 1/2
×
2 −l − 1; j = l − 1/2
54.
a) j = 3/2, mj = 1/2
~3 α
b) hĤSO i = 96m2 ca30

55. The measurements of angular momenta give:


Operator Value Probability
Ŝz ~/2 1/5
−~/2 4/5
L̂z ~ 1/2
−~ 1/2
Jˆz 3~/2 1/10
~/2 4/10
−~/2 1/10
−3~/2 4/10

22
Summary
Commutator relations

[Â, B̂ Ĉ] = [Â, B̂]Ĉ + B̂[Â, Ĉ]


1 h i 1 h h ii
e B̂e− = B̂ + [Â, B̂] + Â, [Â, B̂] + Â, Â, [Â, B̂] + . . .
2! 3!
Time evolution
* +
d 1 D E ∂ Ω̂
|ψ(t)i = e−iĤt/~ |ψ(0)i hΩ̂i = [Ω̂, Λ̂] +
dt i~ ∂t

Uncertainty relations
1
2 |h[Ω̂, Λ̂]i| ≤ ∆Ω ∆Λ
Momentum basis
1  px 
hx|pi = √ exp i
2π~ ~
Translations and rotations
   
ia iα
ÛT (aen ) = exp − en · p̂ ÛR (αen ) = exp − en · Ĵ
~ ~

Harmonic oscillator
r r
~ m~ω †
↠+ â
 
x̂ = p̂ = i â − â
2mω 2
√ √
â|ni = n|n − 1i ↠|ni = n + 1|n + 1i
Angular momentum
Ĵ × Ĵ = i~Ĵ
Jˆ± = Jˆx ± iJˆy Jˆx = 12 (Jˆ+ + Jˆ− ) Jˆy = 2i
1 ˆ
(J+ − Jˆ− )

Jˆ± |j, mi = ~ j(j + 1) − m(m ± 1)|j, m ± 1i = ~ (j ∓ m)(j ± m + 1)|j, m ± 1i


p p

Spin angular momentum


ϕ ϕ
cos θ2 e−i 2 − sin 2θ e−i 2
 
|αn i = +i ϕ
|βn i = ϕ
sin 2θ e 2 cos 2θ e+i 2

Variational principle

hΨ|Ĥ|Ψi
E0 ≤
hΨ|Ψi
Perturbation theory
Time-independent, nondegenerate:
D E E X hψm | Ĥ ′ |ψn i D E
En(1) = ψn Ĥ ′ ψn
(1)
φn = − |ψm i En(2) = ψn Ĥ ′ φ(1)

(0) (0) n
m6=n Em − En

Time-independent, degenerate:
n o
(1)
det H′n − Ej I = 0

Time-dependent:
t 2
Zt Z
1 ′ 1 ′
d(1) dt′ eiωni t Hni

(t′ ) Pf i (t) = 2 dt′ eiωf i t Hf′ i (t′ )

n (t) =
i~ ~
0 0
24
2
|Af i |2 1 − ei(ωf i +ω)t 1 − ei(ωf i −ω)t

Ĥ ′ (t) = Â sin(ωt) =⇒ Pf i (t, ω) = −
4~2 ωf i + ω ωf i − ω