MP463 QUANTUM MECHANICS

Introduction
Quantum theory of angular momentum
Quantum theory of a particle in a central potential
- Hydrogen atom
- Three-dimensional isotropic harmonic oscillator
Non-relativistic quantum theory of electron spin
Addition of angular momenta
Stationary perturbation theory
Time-dependent perturbation theory
Systems of identical particles
REFERENCES
Claude Cohen-Tannoudji, Bernard Liu, and Franck Lalo e
Quantum Mechanics I and II
John Wiley & Sons
Lecture notes - online access:
http://www.thphys.nuim.ie/Notes/MP463/
REQUIREMENTS
The total mark consists of:
Examination (constitutes 80% of the total mark):
duration: 90 minutes,
structure: 3 questions, each with several sub-questions,
requirements: answer 2 (and only 2) of the 3 questions in writing,
maximum mark: 100 points.
Continuous Assessment - 2 quizzes (20% of the total mark):
duration of each quiz: 30 minutes,
maximum mark of each quiz: 10 points.
CHAPTER 0: THE POSTULATES OF QUANTUM MECHANICS
(From Cohen-Tannoudji, Chapters II & III)
FIRST POSTULATE
At a xed time t, the state of a physical system is dened by specifying a ket |(t)
belonging to the state space E.
The state space is a space of all possible states of a given physical system, and it is
a Hilbert space, i.e. it is:
1. a vector space over the eld of complex numbers C
| , |
1
, |
2
E, c
1
, c
2
C (0.1)
| = c
1
|
1
+ c
2
|
2
(0.2)
Denition: A vector space over the eld of complex numbers C is a set of el-
ements, called vectors, with an operation of addition, which for each pair of
vectors | and | species a vector | + |, and an operation of scalar multi-
plication, which for each vector | and a number c C species a vector c |
such that (s.t.)
1) | + | = | + |
2) | + (| + |) = (| + |) + |
3) there is a unique zero vector s.t. | + 0 = |
4) c(| + |) = c | + c |
5) (c + d) | = c | + d |
6) c(d |) = (cd) |
7) 1. | = |
8) 0. | = 0
Example: a set of N-tuples of complex numbers.
2. with an inner (scalar) product.
Dirac bra-ket notation:
| , | E (0.3)
| C (0.4)
A bra | is the adjoint of a ket |, e.g.
if | = c
1
|
1
+ c
2
|
2
, (0.5)
then | = c

1
| + c

2
| (0.6)
We call |
1
and |
2
a basis (or basis elements) of E if and only if
span{|
1
, |
2
} = E (0.7)
and

i
|
j

=
i j
(0.8)
where
i j
is the Kronecker delta-symbol.
3. And with a norm and metric induced by the inner product.
(a) Norm:
e.g.

i
|
j

=
i j
i.e. (0.9)

1
|
1

1/2
=
1
= 1 (0.10)
the norm of |
1

If the norm is 1, the state is normalized, i.e. its length equals 1.

Two vectors are orthogonal if their inner product is zero. Mutually orthogonal
vectors of unit length (norm) are called orthonormal.
(b) Metric: a metric is a map which assigns to each pair of vectors |, | a
scalar 0 such that
i. (| , |) = 0 iff | = |;
ii. (| , |) = (| , |)
iii. (| , |) (| , |) + (| , |) (triangle identity)
We say that the metric is induced by the norm if
(| , |) = | | (0.11)
So the Hilbert space is normed and a metric space. What else?
4. It is also a complete space so every Cauchy sequence of vectors, i.e.
|
n
|
m
0 as m, n (0.12)
converges to a limit vector in the space.
(We need this condition to be able to handle systems with innite-dimensional
Hilbert spaces, i.e. with innite degrees of freedom.)
Can we be more concrete about quantum states? What really is a ket |?
Now, we need the concept of representation.
Let us say we have the Hilbert space E and the basis
B = {|
1
, |
2
} (0.13)
and we have a ket
| E (0.14)
which we wish to express in the representation given by the basis B.
We use the completeness relation

i
|
i

i
| =

1 (0.15)
as follows
| =

i
|
i

i
|

a numberC
(0.16)
=

i
c
i
|
i
(0.17)
Our state becomes a specic superposition of the basis set elements, i.e. we have
expanded | in terms of {|
i
}.
What about a representation in a continuous case (e.g. a free particle)?
The completeness relation:
The coordinate operator

X has the spectral decomposition

X =

x |x x| dx (0.18)
where x are eigenvalues and |x are eigenstates, i.e.

X |x = x |x (0.19)
Then the completeness relation is

|x x| dx =

1 (0.20)
Coordinate representation
| E (0.21)
| =

|x x| dx
=

(x) |x dx (0.22)
{(x)} are coefcients of the expansion of | using the basis given by the eigenvec-
tors of the operator

X, called wavefunction
Inner product in coordinate representation

1
|
2
=

1
(x)
2
(x) dx (0.23)
SECOND POSTULATE
Every measurable physical quantity A is described by an operator

A acting on E; this
operator is an observable.

An operator

A : E F such that

=

A| for
| E

domain D(

A)
(0.24)
and

range R(

A)
(0.25)
Properties:
1. Linearity

A

i
c
i
|
i
=

i
c
i

A|
i

2. Equality

A =

B iff

A| =

B| and D(

A) = D(

B)
3. Sum

C =

A +

B iff

C | =

A| +

B|
4. Product

C =

A

B iff

C | =

A

B|
=

A

B|

=

A

(0.26)
5. Functions

A
2
=

A

A, then

A
n
=

A

A
n1
and if a function f () =

n
a
n

n
, then by
the function of an operator f (

A) we mean
f

n
a
n

A
n
(0.27)
e.g.
e

A
=

n=0
1
n!

A
n
(0.28)
Commutator and anticommutator
In contrast to numbers, a product of operators is generally not commutative, i.e.

A

B

B

A (0.29)

For example: three vectors |x, |y and |z and two operators

R
x
and

R
y
such that:

R
x
|x = |x ,

R
y
|x = |z ,

R
x
|y = |z ,

R
y
|y = |y ,

R
x
|z = |y ,

R
y
|z = |x
(0.30)
then

R
x

R
y
|z =

R
x
|x = |x (0.31)

R
y

R
x
|z =

R
y
|y = |y (0.32)

An operator

A,

B

=

A

B

B

A is called commutator.
We say that

A and

B commute iff

A,

B

= 0 in which case also

f (

A), f (

B)

= 0.
An operator

A,

B

=

A

B +

B

A is called anticommutator.
Basic properties:

A,

B

B,

A

(0.33)

A,

B

B,

A

(0.34)

A,

B +

C

A,

B

A,

C

(0.35)

A,

B

C

A,

B

C +

B

A,

C

(0.36)
the Jacobi identity:

A,

B,

C

B,

C,

A

C,

A,

B

= 0 (0.37)
Types of operators (examples)
1.

A is bounded iff > 0 such that

A|

| for all | D(

A). Inmum of
is called the norm of

A
2.

A is symmetric if

1
|

A
2

A
1
|
2

for all |
1
, |
2
D(

A).
3.

A is hermitian if it is bounded and symmetric.
4. Let

A be a bounded operator (with D(

A) dense in E); then there is an adjoint operator

A

such that

1
|

A

A
1
|
2

(0.38)
i.e.

1
|

A

2
|

A
1

(0.39)
for all |
1
, |
2
D(

A).
Properties:

(0.40)

=

A (0.41)

A +

B

=

A

+

B

(0.42)

A

B

=

B

(the order changes) (0.43)

(0.44)
How can we construct an adjoint?
E.g. Let us have an operator in a matrix representation (so it is also a matrix)
then

A
T

= transpose & complex conjugation (0.45)

5.

A is selfadjoint if

A

=

A.
This is the property of observables!
Their eigenvalues are real numbers, e.g.

X |x = x |x
6.

A is positive if |

A| 0 for all | E
7.

A is normal if

A

A

=

A

A i.e.

A,

A

= 0

commutator
8. Let

A be an operator. If there exists an operator

A
1
such that

A

A
1
=

A
1

A =

1
(identity operator) then

A
1
is called an inverse operator to

A
Properties:

A

B

1
=

B
1

A
1
(0.46)

1
=

A
1

(0.47)
9. an operator

U is called unitary if

U

=

U
1
, i.e.

U

U

=

U

U =

1.
Formal solution of the Schr odinger equation leads to a unitary operator: if

H is
the Hamiltonian (total energy operator),
i
d
dt
|(t) =

H |(t) (0.48)

t
0
d

(t

|(t

)
=
i

t
0

Hdt

(0.49)
If the Hamiltonian is time independent then
|(t) = e

Ht
|(0) =

U |(0) (0.50)
10. An operator

P satisfying

P =

P

=

P
2
is a projection operator or projector
e.g. if

is a normalized vector then

P
k
=

(0.51)
is the projector onto one-dimensional space spanned by all vectors linearly de-
pendent on

.
Composition of operators (by example)
1. Direct sum

A =

B

C

B acts on E
B
(2 dimensional) and

C acts on E
C
(3 dimensional)
Let

B =

b
11
b
12
b
21
b
22

and

C =
_

_
c
11
c
12
c
13
c
21
c
22
c
23
c
31
c
32
c
33
_

_
(0.52)

A =
_

_
b
11
b
12
0 0 0
b
21
b
22
0 0 0
0 0 c
11
c
12
c
13
0 0 c
21
c
22
c
23
0 0 c
31
c
32
c
33
_

_
(0.53)
Acts on E
B
E
C
Properties:
Tr

B

C

= Tr

+ Tr

(0.54)
det

B

C

= det

det

(0.55)
2. Direct product

A =

B

C:
| E
B
, | E
C
, | E
B
E
C
(0.56)

A| =

B

C

(| |)

|| to simplify the notation

(0.57)
=

B|

C | (0.58)

A = (0.59)
_

_
b
11
c
11
b
11
c
12
b
11
c
13
b
12
c
11
b
12
c
12
b
12
c
13
b
11
c
21
b
11
c
22
b
11
c
23
b
12
c
21
b
12
c
22
b
12
c
23
b
11
c
31
b
11
c
32
b
11
c
33
b
12
c
31
b
12
c
32
b
12
c
33
b
21
c
11
b
21
c
12
b
21
c
13
b
22
c
11
b
22
c
12
b
22
c
13
b
21
c
21
b
21
c
22
b
21
c
23
b
22
c
21
b
22
c
22
b
22
c
23
b
21
c
31
b
21
c
32
b
21
c
33
b
22
c
31
b
22
c
32
b
22
c
33
_

_
(0.60)
Eigenvalues and eigenvectors
Solving a quantum mechanical system means to nd the eigenvalues and eigenvec-
tors of the complete set of commuting observables (C.S.C.O.)
1. The eigenvalue equation

A|

eigenvalue
|

eigenvector
(0.61)
If n > 1 vectors satisfy the eigenvalue equation for the same eigenvalue , we
say the eigenvalue is n-fold degenerate.
2. The eigenvalues of a self-adjoint operator

A, which are observables and repre-
sent physical quantities, are real numbers

|

A

(0.62)
=

(0.63)
=

R (0.64)
3. Eigenvectors of self-adjoint operators corresponding to distinct eigenvalues are
orthogonal.
Proof: if is also an eigenvalue of

A then

|

A

(0.65)
and also

|

A

|

A

(0.66)
=

(0.67)
which implies

= 0 (0.68)
4. Matrix representation
Operator is uniquely dened by its action on the basis vectors of the Hilbert
space.
Let B =

be a basis of E (= D(

A))

(0.69)
=

k
A
k j

(0.70)
where A
k j
=

are the matrix elements of the operator

A in the matrix
representation given by the basis B.
For practical calculations

A =

k j

k j
A
k j

(0.71)
5. Spectral decomposition (of eigenrepresentation)
Assume that the eigenvalues of

A dene a basis B =

,
then A
k j
=

=
j

k j
.
Operator in this basis is a diagonal matrix with eigenvalues on the diagonal

A =

k j
A
k j

(0.72)
=

(0.73)
=

j

E
j
(0.74)

E
j
is a projector onto 1-dim. space spanned by

Spectral decomposition!
Generalization to the continuous spectrum

A| = | (0.75)

= (

) (0.76)
-function [Cohen-Tannoudji II Appendix II]
Spectral decomposition

A =

max

min
| | d (0.77)
Completeness relation

max

min
| | d =

1 (0.78)
Wavefunction
() = | (0.79)
the inner product

1
|
2
=

max

min

1
()
2
() d (0.80)
Coordinate and momentum operators
In coordinate representation (x-representation)

X =

x |x x| dx spectral decomposition (0.81)

and

|x x| dx =

1 completeness relation (0.82)
| =

|x x| dx =

(x) |x dx (0.83)
What about

P (momentum op.)?
It has to satisfy the canonical commutation relation

X,

P

| =

X

P|

P

X | (0.84)
= i | (0.85)
which in coordinate representation is
x

P
(x)
(x)

P
(x)
x(x) = i(x) (0.86)
This is satised by

P
(x)
= i

x
(0.87)
In momentum representation
B = {| p} :

P =

p | p p| dp (0.88)
and

X = i

p
(0.89)
More on coordinate and momentum representation
Coordinate representation

X =

x |x x| dx

X |x = x |x (0.90)

P
(x)
= i

x

X,

P

= i (0.91)
For all p R, there is a solution to the eigenvalue equation
i
d
dx

p
(x) = p
p
(x) (0.92)
where
p
(x) is the eigenstate of the momentum operator (in coordinate representa-
tion) corresponding to eigenvalue p

P| p = p | p | p =

|x x| p dx =

p
(x) |x dx (0.93)
and every solution depends linearly on function

p
(x) =
1

2
e
i

px
= x| p (0.94)
which satises the normalization condition

(x)
p
(x) dx =

p p

(0.95)
Similarly

p
(x) dp =

x x

(0.96)
Momentum representation

P =

p | p p| dp (0.97)
The completeness relation

| p p| dp =

1 (0.98)
| =

| p p| dp =

momentum representation

(p)
(p) | p dp (0.99)
How is the wavefunction
(p)
(p), which describes the ket | in the momentum rep-
resentation, related to (x) which describes the same vector in the coordinate repre-
sentation?

(p)
(p) =

p|x x| dx =
1

px
(x) dx (0.100)

(p)
(p) is the Fourier transform of (x)
(x) is the inverse F.T. of
(p)
(p)
(x) =
1

e
+
i

px

(p)
(p) dp (0.101)
(Cohen-Tannoudji Q.M. II Appendix I)
The Parseval-Plancharel formula

(x)(x) dx =

(p)
(p)
(p)
(p) dp (0.102)
F.T. in 3 dimensions:

(p)

p

=
1
(2)
3/2

pr

d
3
r (0.103)
-function
1. Principal properties
Consider

(x):

(x) =

for

2
x

2
0 for |x| >

2
(0.104)
and evaluate

(x) f (x) dx ( f (x) is an arbitrary function dened at x = 0)

if is very small ( 0)

(x) f (x) dx f (0)

(x) dx (0.105)
= f (0) (0.106)
the smaller the , the better the approximation.
For the limit = 0, (x) = lim
0

(x).

(x) f (x) dx = f (0) (0.107)

More generally

x x
0

f (x) dx = f

x
0

(0.108)
2. Properties
(i) (x) = (x)
(ii) (cx) =
1
|c|
(x)
and more generally

g(x)

j
1

x
j

x x
j

(0.109)
{x
j
} simple zeroes of g(x) i.e. g(x
j
) = 0 and g

(x
j
) 0
(iii) x(x x
0
) = x
0
(x x
0
)
and in particular x(x) = 0
and more generally g(x)(x x
0
) = g(x
0
)(x x
0
)
(iv)

(x y)(x z) dx = (y z) (0.110)
3. The -function and the Fourier transform

(p)
(p) =
1

px
(x) dx (0.111)
(x) =
1

e
i

px

(p)
(p) dp (0.112)
The Fourier transform
(p)
(p) of (x x
0
):

(p)
(p) =
1

px

x x
0

dx (0.113)
=
1

2
e

px
0
(0.114)
The inverse F.T.

x x
0

=
1

e
i

px

(p)
(p) dp (0.115)
=
1

e
i

px
1

2
e

px
0
dp (0.116)
=
1
2

e
i

p(xx
0
)
dp (0.117)
=
1
2

e
ik(xx
0
)
dk (0.118)
Derivative of (x)

x x
0

f (x) dx = (0.119)

x x
0

(x) dx = f

x
0

(0.120)
THIRD POSTULATE
(Measurement I)
The only possible result of the measurement of a physical quantity A is one of the
eigenvalues of the corresponding observable

A.
FOURTH POSTULATE
(Measurement II)
1. a discrete non-degenerate spectrum:
When the physical quantity A is measured on a system in the normalized state
|, the probability P(a
n
) of obtaining the non-degenerate eigenvalue a
n
of the
corresponding physical observable

A is
P(a
n
) = |u
n
||
2
(0.121)
where |u
n
is the normalised eigenvector of

A associated with the eigenvalue a
n
.
2. a discrete spectrum:
P(a
n
) =
g
n

i=1

u
i
n
|

2
(0.122)
where g
n
is the degree of degeneracy of a
n
and {

u
i
n

} (i = 1, . . . , g
n
) is an or-
thonormal set of vectors which forms a basis in the eigenspace E
n
associated
with the eigenvalue a
n
of the observable

A.
3. a continuous spectrum:
the probability dP() of obtaining result included between and + d is
dP() = |v

||
2
d (0.123)
where |v

is the eigenvector corresponding to the eigenvalue of the observ-

able

A.
FIFTH POSTULATE
(Measurement III)
If the measurement of the physical quantity A on the system in the state | gives
the result a
n
, the state of the system immediately after the measurement is the mor-
malized projection

P
n
|

|

P
n
|
=

P
n
|

P
n
|

(0.124)
of | onto the eigensubspace associated with a
n
.
SIXTH POSTULATE
(Time Evolution)
The time evolution of the state vector |(t) is governed by the Schr odinger equation
i
d
dt
|(t) =

H(t) |(t) (0.125)
where

H(t) is the observable associated with the total energy of the system.
-
Classically
H(r, p) =
p
2
2m
+ V

r

(0.126)
Quantum mechanics
r

R
p

P
_

H =

P
2
2m
+ V

(0.127)
Canonical quantization (in the coordinate rep.)

R r (0.128)

P
i
i

x
i
=

i
(0.129)

H =

2
2m

kinetic energy
+ V

r

potential energy
(0.130)