Lecture # 2

Today’s Program
1. Recap: Classical States, Hamiltonians and time evolution
2. First postulate – The description of a state of a system.
3. Second postulate – physical quantities.
4. Linear operators.
5. Finding the eigenvectors and eigenvalues of operators.
6. Hermitian operators. Definition and characteristics.
7. Third postulate - The measurement of physical quantities.
8. Sixth postulate – Time evolution of the system.
9. How to construct the QM Hamiltonian?
10. Define Hermitian operator – properties of Hermitian operators.
11. Examples of two observables X and P.
12. How to construct observable operators?
13. Sixth postulate – time evolution of the system.
14. Example: how to construct the QM Hamiltonian for a “free particle”?
15. Finding the wave function and time evolution for a free particle.
16. Second example – particle in an infinite potential well

References for Today’s lecture:

1. Quantum Mechanics, Cohen Tannoudji, Chapters 2-3.

2. Linear Algebra, Schaum Series
3. Quantum Chemistry Ch. 6

Mathematical concepts in today’s lecture:

1. vector spaces, wavefunctions(vectors), operators, linear operators (matrices).
2. Hermitian operators, eigenfunctions (eigenvectors), eigenvalues.
3. Properties of Hermitian operators, inner products (scalar products), expanding
functions in terms of basis functions.
4. Solving simple partial differential equations using separation of variables method.
Physical theory:
1. How do you represent a state in QM?
2. How do you represent a physical quantity?
3. What are the possible outcomes of a measurement?
4. How do we determine the time evolution of our state?

Questions you should be able to answer by the end of today’s lecture:

1. How would you know if a collection of objects is a vector space?
2. What is the equivalent of a projection in function space?
3. What are the special properties of hermitian operators.
4. How do we represent in QM the basic position, X and momentum, P observables?
5. How to construct quantum mechanical observables (i.e. physical quantities)?
The postulates of quantum mechanics

First Postulate: The state of a physical system at time t0 is defined by specifying its

state vector ψ ( t0 ) which belongs to a state space. The state space is a vector space.

Comments:
One can represent states in different bases in particular in some cases one can represent a
r
state vector with a function ψ ( r , t0 ) which is sometimes called a wave function. This

wavefunction belongs to a wave function space which means that it has certain
restrictions:
(a) single valued
(b) nowhere infinite (at infinity as well as elsewhere)
(c) continuous
(d) piecewise continuous first derivative
Side: Vector space (or how to determine if a collection of objects are a vector space):
The following defines the notion of a vector space V where K is a field of scalars.
Definition: Let V be a nonempty set with two operations:
(e) Vector Addition: This assigns to any u , v ∈ V a sum u + v ∈ V
(f) Scalar Multiplication: This assigns to any u ∈ V k ∈ K a product ku ∈ V
V is called a vector space if the following axioms hold for any vectors u , v, w ∈V

(1) ( u + v ) + w = u + ( v + w )

(2) There exits a zero vector such that u + 0 = 0 + u = u ∀u ∈ V

(3) There exists a –u vector such that u + ( −u ) = ( −u ) + u = 0 ∀u ∈ V

(4) u + v = v + u
(5) k ( u + v ) = ku + kv where k is a scalar

(6) ( a + b ) u = au + bu where a,b are scalars

(7) ( ab ) u = a ( bu ) where a,b are scalars

(8) 1u = u
Important comment
It is useful to think of the wave function as a vector which belongs to a vector space
exactly like a 3D vector belongs to the 3D vector space. A linear combination of wave
functions is also a wave function.
Definition:
The scalar or inner product of two wave functions is,

ψ ( x) ϕ ( x) ≡ (14
ψ ( x ) ,ϕ ( x ))
4244 3
≡ ∫ψ ( x ) ϕ ( x )dx
•

different notation same meaning

in particular,

ψ ( x ) ψ ( x ) ≡ ∫ ψ ( x ) dx
2

two functions ψ ( x ) , ϕ ( x ) are orthogonal if

ψ ( x ) ϕ ( x ) ≡ ∫ψ ( x ) ϕ ( x )dx = 0
•

If we think of our wavefunctions as vectors the inner product between vectors is,
1
[1 2 1] ⋅ 1 = 1 + 2 + 1 = 4
1

Second Postulate: Every measurable physical quantity a is described by an operator Â

acting on the state vector space. This operator is Hermitian and is called an observable.

r
Definition: A linear operator A is, a rule which associates with every function ψ ( r , t )
r
another function ψ ′ ( r , t ) the correspondence being linear:
r r
ψ ′ ( r ) = Aψ ( r )
r r r r
A  λψ1 1 ( r ) + λ2ψ 2 ( r ) 
 = λ1 Aψ 1 ( r ) + λ2 Aψ 2 ( r )
example: an example of a linear operator is the differentiation operator
∂
A=
∂x

If we again look at our vector analogy, a linear operator A is, a rule which associates with
every function u another function v the correspondence being linear:
 v = Au
A [ λ1u1 + λ2u2 ] = λ1 Au1 + λ2 Au2
r
Definition: ϕ ( r ) is said to be an eigenfunction of the linear operator A if:
r r
Âϕ ( r ) = λϕ ( r )

where λ is a complex number (a+ib) which is called the eigenvalue of A.

Finding the eigenvectors and eigenvalues of a linear operator,

1 −i   a  a 
i 1   b  = λ  b 
    
1 − λ −i   a  1 − λ −i
 i = → = → =0
1 − λ   b 
0 det( A) 0
 i 1− λ
(1 − λ ) − 1 = 0 → λ1 = 0, λ2 = 2
2

1 − 0 −i   a  i 
 i    = 0 → v1 =  
 1 − 0 b  1
 −1 −i   a  i 
 i −1  b  = 0 → v2 =  −1
    

Definition: An operator A is Hermitian if A adjoint equals A,

A† = A
the dagger symbol is defined in the following way
A†ij = A• ji
Example of the adjoint of an operator which is not Hermitian:
 1 1
B= 
1 + 2i 5
1 1 − 2i 
B† = 
1 5 
Examples of an operator which is Hermitian:
 1 i
A= 
 −i 1
Important Characteristics of Hermitian Operators
(i) All the eigenvalues of an Hermitian operator are real.
(ii) Eigenvectors belonging to different eigenvalues are orthogonal.
(iii) An Hermitian operator operating on a space of dimension N will always have N
linearly independent eigenvectors.

The X and P operators in wavefunction space

r
Statement: with the position r ( x, y , z ) of the particle is associated the observable
r r
R ( X , Y , Z ) with the momentum of a particle p ( px , py , pz ) is associated the observable
r
P ( Px , Py , Pz ) .
r
In wave function space ψ ( r ) these operators are defined in the following way:

hr r hr r
Pˆ = ∇ → Pˆψ ( r ) = ∇ψ ( r )
i i
r r r
Rˆ = r → Rˆψ ( r ) = rˆψ ( r )

Xˆψ ( x ) = xψ ( x )
r r r
Rˆψ ( r ) = rψ ( r )

h ∂
Pˆxψ ( x ) = ψ ( x)
i ∂x
r hr r
Pˆψ ( r ) = ∇ψ ( r )
i
Comment: Classically any physical quantity a can be expressed in terms of the basic
variables r and p.

How to construct observable operators?

We are now going to discuss how to construct for a physical quantity a already defined
in classical mechanics the operator  which describes it in quantum mechanics.

Rule: To obtain the observable A from the classical analogue one simply replaces in the
expression for A(r,pt) the observables Rˆ , Pˆ .
Sixth Postulate: Comment: The time evolution of the state vector ψ ( t ) is governed by

the Schrodinger equation:

d
ih ψ ( t ) = Hˆ ( t ) ψ ( t )
dt
where H is the observable associated with the total energy of the system. H is called the
Hamiltonian operator of the system and is related to the classical Hamiltonian.

r
Comment: The time evolution of the wave function ψ ( r , t ) is governed by the

Schrodinger equation (see CT complement DII ):

∂ r r
ih ψ ( r , t ) = Hˆ ψ ( r , t )
∂t
where H is the observable associated with the total energy of the system. H is called the
Hamiltonian operator of the system and is related to the classical Hamiltonian.

First Example: The Hamiltonian of a free particle:

r r
p2 P2
H classical = →H =ˆ
2m 2m
r r
P⋅P h r h r  ∂ ∂ ∂  ∂ ∂ ∂ 
H=
ˆ = ∇ ⋅ ∇ = − h 2  xˆ + yˆ + zˆ  ⋅  xˆ + yˆ + zˆ 
2m i i  ∂x ∂y ∂z   ∂x ∂y ∂z 
for the case of a 1D problem
The equation for the time evolution of the wave function is the following:

h 2 ∂ ψ ( x, t ) ∂ψ ( x, t )
2

− = i h
2m ∂x 2 ∂t
we have obtained a differential equation the method to solve this type of equation is to
perform a separation of variables
ψ ( x, t ) = φ ( x ) ξ ( t )

substituting in the above equation gives,

h2 1 ∂ φ ( x ) 1 ∂ξ ( t )
2

− = ih =E
2m φ ( x ) ∂x 2
ξ ( t ) ∂t
The time dependent part becomes:
dξ ( t ) E E
−i t
+i ξ (t ) = 0 → ξ (t ) = e h
dt h
The spatial part becomes,

∂ 2φ ( x ) 2m
+ Eφ ( x ) = 0 → φ ( x ) = ae + ikx + be−ikx
∂x 2
h 2

2m
k= E
h2
The entire solution is,
E

( )e
−i t
ψ ( x, t ) = ae + ikx
+ be − ikx h

We have now obtained a form for the wave function:

Let us now check and see if this wave function is an eigenfunction of the energy operator
which we have called the Hamiltonian:
Remember that in order for a function u ( x, t ) to be defined as an eigenfunction of a

particular operator it has to satisfy the following relation:

ˆ ( x, t ) = λ u ( x, t )
Hu

Let us now check if our solution for ψ ( x, t ) is indeed an eigenvector of the Hamiltonian,

h 2 ∂ ψ ( x, t )
2

− = λψ ( x, t )
2m ∂x 2
h 2 ∂ 2 ikx − i h t h2
E E E
2 ikx − i h t −i t
− e e =− ( ik ) e e = Ee e h ikx

2m ∂x 2 2m
Second example: particle in an infinite potential well:
I] The system:
A particle of mass 2m in a potential well:

II] The classical energy function of the system:

p2
H ( x, p ) = +V ( x)
2m
where the potential energy is defined as follows
 d d
 0 − <x<
V ( x) =  2 2
∞ d d
x < − or x >
 2 2
III] Obtaining the QM Hamiltonian operator:

h2 ∂ 2
ˆ (
H ( x, p ) → H X , P =
ˆ ˆ
2m
)
Pˆ 2 ˆ
+V ( x) = −
2m ∂x 2
+ Vˆ ( x )

note: for regions where V=infinity there can be no particle.

h2 ∂ 2
( )
Hˆ Xˆ , Pˆ = −
2m ∂x 2
Defined an inner product between two functions

(ϕ ( x ) ,ψ ( x ) ) = ∫ ϕ ( x ) ψ ( x ) dx
•

Remind ourselves of the geometrical interpretation (in 2D for simplicity)

Look at two vectors ψ , ϕ (psi and phi), the inner product results in a number (could
be complex scalar) tells us what the projection of one on the other is. Now the
projection is independent of the basis which you decide to represent your vector in.
ϕ ψ = (ϕ ,ψ ) = c

how do we represent a vector ψ in a particular basis:

we choose a particular set of vectors which span the vector space ϕ1 , ϕ 2 usually we
choose basis set to be orthonormal.
then we find the projection of ψ in the direction of each basis vector.

ϕ1 ψ = (ϕ1 ,ψ ) = c1
ϕ 2 ψ = (ϕ 2 ,ψ ) = c2

Write the original function as a linear combination of the basis vectors.

ψ = c1ϕ1 + c2ϕ 2
In general
N
ψ = ∑ ciϕi
i =1

Finding the eigenvectors and eigenvalues of operators, discuss the geometrical

interpretation of eigenvectors and eigenvalues – scaling.
Hermitian operators. definition and characteristics in function space.
We said last time that an operator (on either vector space or function space) is defined in
the following way:
Aˆψ ( x ) = ψ ′ ( x ) → Aˆ ψ = ψ ′

An hermitian operator was defined as:

Aˆ † = Aˆ
in matrices it was pretty straight forward:

Aˆ = Aij
∗
Aˆ † = Aij

Define a matrix element of an operator:

ϕ Aˆ ψ = ∫ ϕ ( x ) Aˆψ ( x ) dx
∗

Basically for a basis set ϕ i where i=1...n

A is a matrix

Aij = ϕi Aˆ ϕ j = ∫ ϕi ( x ) Aˆϕ j ( x ) dx
∗

The adjoint is:

( ∫ψ ( x ) Aˆϕ ( x ) dx )
∗ ∗
∗
ϕ Aˆ † ψ = ψ Aˆ ϕ =

Therefore an hermitian matrix is:

( )
∗ ∗

∫ψ ( x ) Aˆϕ ( x ) dx = ∫ ϕ ( x ) Aˆψ ( x ) dx = ϕ Aˆ ψ
∗ ∗
ϕ Aˆ † ψ = ψ Aˆ ϕ =