Some

Basic Derivations and Proofs in Quantum Mechanics

Indrajit Kamalanathan
University of Leipzig
2015-2016

2.1. INNER PRODUCTS

Let an arbitrary state | , be given as,

! |!

| =

(2.1.)

Then the inner product of | with itself is simply the probability amplitude and its
modulus squared gives the probability.

!

| = !
!

! |!
!

(2.2.)

! ! ! |!

| =
!,!

But, ! ! are orthogonal basis, so their inner products must be,

1,
=
! |! =

0,


Suppose if, = in eqn. (2.3), then it reduces to,

! ! ! |!

| =
!

(2.3.)

(2.4.)

(2.5.)

!!

! !

| =
!

(2.6.)

2.2. OUTER PRODUCTS:

Let an arbitrary state | , be given as,

! |!

| =
!

where |! is some orthonormal basis.

Theorem 2.1: An outer product of any basis state with itself results in an identity operator.

|! ! | =
!

(2.7.)

where is the identity operator

Proof 2.1:

We know that when an identity operator acts on a state, it leaves the state unchanged, i.e.

(2.8.)
| = |


Lets consider the outer product in eqn. (2.7) acting on the arbitrary state | ,

|! ! ! !

|! ! | =
!

(2.9.)

The above equation reduces to,

|! ! | =

! |!

! |!
!!,
!!!" !!!

(2.10.)

! |! = |

|! ! | =
!

(2.11.)

Thus we have proved that any outer product of an orthonormal basis state with itself
results in an identity operator.

2.3. Hermitian Operator:

All operators are generally matrices. A Hermitian operator is one of those matrices
where its complex conjugate transpose equals the original matrix, i.e.,


(2.12.)
= !
!
where, ! = , the conjugated transpose.

For example lets consider the well-known eigenvalue equation,

(2.13.)
| = |
where is the eigenvalue.

Now if we let an arbitrary state | act on eqn. (2.13), we obtain,

| = | = | =
(2.14.)
!!

The above scenario is possible if and only if the operator is Hermitian.

Suppose if we let another arbitrary operator | , act on eqn. (2.13), we obtain,

| = | = |
!!

(2.15.)

One more interesting property of the Hermitian operator is, suppose we take the complex
conjugate of the RHS of eqn. (2.15.), we have

|

= ! | = |

(2.16.)

2.4. Integrals and Inner Products:

So far we have considered only discrete set of states, which exists only as a linear
superposition, i.e.

! |!

| =

The above formulation is valid only if the number of basis states is finite. But there are
situations in quantum mechanics, where particles exist in a continuum of states, i.e. infinite
number of states exists at a single point in space. In that case, the above formulation
changes from being a summation to an integral as follows,

!

| =
!

! |! =
!!

(2.17.)

So an inner product of continuum of states can be represented as,

!

()

| =

(2.18.)

!!

The eqn. (2.18) can only be solved by integration by parts. Here is a small trick to do the
integration by parts. Lets consider the product of two variables (), and
differentiate them,

()
()
()
(2.19.)
=
+

() ()
()
(2.20.)

If we integrate on both sides of eqn. (2.20), we get,

!
!
!
()
()
()

!!
!!
!!
(2.21.)
!!,
!!!" !!!
!"# !!!

So the eqn. (2.21) simply reduces to,

!
!
()
()

(2.22.)

!!
!!
Now we can use the above equation, to test whether an operator is Hermitian or not as
follows.

Let us consider an operator acting on arbitrary state | given by,

(2.23.)
| =
|

Now if we let another arbitrary state | act on above equation we get,

(2.24.)
|| = |
|

If the operator is Hermitian, then

| = |
(2.25.)

Now let us take the integral of both sides and check whether they are equal,

!

()
| =
| =
()

(2.26.)

!!

(2.27.)
| =
| =

!!
By making use of the identity in eqn. (2.22), we can manipulate the RHS of eqn. (2.27) to
get,

!
!

(2.28.)

!!
!!

Now if we take complex conjugate the RHS of eqn. (2.28), we get,

!

()

| =
| =
()

(2.29.)

!!

Thus we have proved from eqn. (2.26) and eqn. (2.29), that = !" is indeed a Hermitian
operator, i.e.,
| = |

2.4. Derivation of Momentum Operator:

!
Let us consider an arbitrary Hermitian operator = !" which satisfies the following
eigenvalue equation,
(2.30.)
| = |
where k is some eigenvalue.

If we substitute the value for in eqn. (2.30), we get

(2.31.)

| = |

(2.32.)
| = |

The solution for differential eqn. (2.32.),

(2.33.)
| = !"#

The eqn. (2.33) is nothing but the wavefunction given by,

(2.34.)
| = !"# = + sin ()

where is the wavenumber, given by,

!!
!

(2.35.)

Also we know from the de Broglies equation, the wavelength is given by,

!

= !

where is the momentum.

Now the wavenumber can be rewritten as,

!!"
!

(2.36.)

=
!

(2.37.)

The eqn. (2.33.) can be rewritten as, | = ! ! and on differentiating it with respect to ,
we get,

(2.38.)
| = |

By rearranging the above equation a little bit we obtain the momentum operator,

(2.39.)
| = |

(2.40.)
| =
| = |

where is the momentum operator and is the associated eigenvalue.

2.5. Commutator Relations:

Let us consider two operators acting on an arbitrary orthogonal basis |

| = |
and
| = |
where and are some eigenvalues associated with their respective operators.
Now if we let act on eqn. (2.41) and let act on eqn. (2.42), we get,

| = | = | = |
Similarly,
| = | = | = |

Now if we subtract, eqn. (2.44) from eqn. (2.43) we get,

| = |
!!,
!,!

! !,!

, i.e.
(2.41.)
(2.42.)

(2.43.)
(2.44.)

(2.45.)

Thus we have the commutation relation,

, = =

(2.46.)

It is worth noting, that commutation relation , does not necessarily lead to zero at all
times. This can be demonstrated using the Heisenbergs uncertainty principle in the next
section.

2.6. Heisenberg Uncertainty Principle:

Heisenbergs uncertainty principle states that it is impossible to measure a particles
position and momentum along one direction at the same time.

Proof:

Let us consider the position operator and momentum operator acting on an arbitrary
orthogonal basis state | given by,

(2.47.)
| = |
and

(2.48.)
| = | = |

Now we can check whether position operator and momentum operator acting on |
commutes, i.e.
?

, = = 0
Now lets derive this commutation relation,

| = | |

| +
| + |

(2.49.)
(2.50.)

(2.51.)

!!

So we have arrived at the relation,

| = |
(2.52.)
As can be seen from the above relation, the commutators do not necessarily lead to zero
and because of this reason it is impossible to measure the position and momentum of a
particle at the same time, there by proving the Heisenbergs uncertainty principle, i.e.

, =

(2.53.)

2.7. Commutation Relations of Pauli Matrices:

One of the consequences of the Heisenbergs uncertainty principles is that, it is impossible
to simultaneously measure the spin of an electron along two directions.

Proof:

We know the Pauli matrices for the electron spin along x-, y- and z- axes are given by

0 1
! =

(2.54.)
1 0

0
! =

(2.55.)
0

1 0
! =

(2.56.)
0 1
Also, we know that,

, = ,
(2.57.)

Since Pauli Matrices are essentially operators, they must commute. Lets find out what
happens when two Pauli matrices commute.

Suppose we want to measure the electron spin along and direction simultaneously, and
then we have,

! , ! = (! ! ! ! )
(2.58.)

0 1 0
0 0 1
! ! ! ! =

(2.59)
1 0 0
0 1 0

0
0
0
1 0
=

=2
= 2


0
0
0
0 1
!!!

, = ( ) =

(2.60)

Similarly if we want to measure the electron spin along and direction simultaneously,

! , ! = (! ! ! ! )
(2.61.)

0 1 0
1 0
0
! ! ! ! =

(2.62.)
0 0 1
0 1 0

0
0
0 1
=

= 2


0
0
1 0
!!!

, = ( ) =

(2.63.)

For the sake of completeness, lets also measure the electron spin along and direction
simultaneously

! , ! = (! ! ! ! )
(2.64.)

0 1 1 0
1 0
0 1
! ! ! ! =

(2.65.)
1 0 0 1
0 1 1 0

2 0
0 1
0 1

=
= 2!
1 0
1 0
0

!!!

, = =

(2.66.)

As can be seen from equations (2.60.), (2.63.) and (2.66), the commutation relations for all
three Pauli Matrices are non-zero. Hence we have proved that the electron spin along any
two directions cannot be measured simultaneously.

2.8. Energy Operators and Time Independent Schrodinger Equation:

Starting from the well known eigenvalue equation,

| = |

where is some eigenvalue for the operator, .

Suppose we assume that the operator is a Hamiltonian and it gives the total energy of
the system, i.e.,

!

!"#$%"& !"!#$%

()

(2.67.)

!"#$%#&'( !"!#$%

!
Also we know that the momentum operator is, | = !", so the eqn. (2.67) becomes,

+ ()

+ =

(2.68.)

!! ! !

Now that we have an energy operator, = !! !! ! + () and if we let it act on some

state | , then it must give an eigenvalue for energy ( = ), i.e.

(2.69.)
| = |

Plugging in the value for from eqn. (2.68.) into eqn. (2,69), we have,


+ () | = |
(2.70.)

Thus we have derived the time independent Schrodinger equation.

2.10. Time Evolution of Unitary Operators:

Let us consider two arbitrary orthogonal basis states | and | that evolves over a period
of time .

!
(2.71.)
|
|

!
(2.72.)
|
|

And the corresponding bra vector of | is given by

!
(2.73.)
|
| !

Then the time evolution of inner product is given by,

|

| ! |

(2.74.)

!!

One of the postulates in quantum mechanics tells us that, even though the states
| and | may evolve over time individually, their inner products remains unchanged with
time evolution, i.e. they remain orthogonal after any amount of time. This postulate leads
to a new class of operator called the unitary operator, .

An operator is called the unitary operator when it satisfies the condition,

(2.75.)
! = ! =

In other words, when an operator acts on the transposed conjugate of itself must result in
an identity operator.

In the following section, we investigate the consequences of the time evolution of unitary
operator at different times. Consider an arbitrary orthogonal basis state |() that evolves
with time. Let |(! ) be the state at time = 0, then its evolution over a period of time
is given by,

(2.76.)
| ! ; = ()|(! )

If there is no evolution of time, then

(2.77.)
| ! ; ! = (! )|(! ) = |(! ) = |(! )

Because, if no time has lapsed, the state |(! ) remains unchanged.

Now lets consider a situation, where there is an infinitesimal change in time, = , then

(2.78.)
| ! ; = ()|(! )

The unitary operator at time can be can be calculated from the time dependent
Hamiltonian and it reads,

!
(2.79.)
= !! !

The exponential of a matrix is defined by the Taylor series as,

!
!
! = 1 + + !! ! + !! ! +
(2.80.)

Using eqn. (2.80) we can write () as,

!

= !! !" =

!!

(2.81.)

where we have used the identity operator in the place of 1 in eqn. (2.80) and also we
have ignored all higher order term since is very small.

Using the identity in eqn. (2.75), we can prove that the Hamiltonian is also Hermitian,

! = +

!! !

!!

(2.82.)

 ! = +

!"#

!"#

(! ) +

!" !

!
!
!"# !" !"#$%&'
!"#$% !" !" !"#$
!"#$$

(! ) = 0

! =

(2.83.)

2.11. Time Dependent Schrodinger Equation from Unitary Operators:

Lets consider an arbitrary basis state |() going through an time evolution at time,
= + , then,


(2.84.)
| ; + = ()|()

But we already know, =

| ; + =

!!

!!

, so eqn. (2.78) becomes,

|() = |()

| ; + |() =

!!

lim!"!

(|! ! ;!!!" ) (|!(!) )

!"

!|!(!)
!"

|() =

!!

!!

|()

|()

!!

|()

|()

|()

= |()

(2.85.)

(2.86)

Thus we have derived the time dependent Schrodinger equation from the definition of a
time evolving unitary operator.

2.12. Expectation Value :

Expectation value is quite akin to the classical meaning of an average. In mathematical
terms, one can calculate for example, the number of heads or tails, a person can get by
tossing a coin six times by,

= ! ! (! )
(2.87)

where ! is the number of outcomes and (! ) is the probability of getting that outcome.

Let an arbitrary state | be given by,

! |!

| =

(2.88.)

Let be an operator acting on | , such as,

! ! |!

| = ! | =

(2.89.)

Then, the expectation value is given by,

!

= || = |! | = ! |
!

! ! |!
!

(2.89.)

! ! ! ! |!

(2.90.)

!!,
!" !!!

!,!

= || =

( )

. .

( )

(2.91.)

Thus we have derived an expression for the expectation value .

2.13. Time evolution of basis states:

Let an arbitrary state | be given by,

! |!

| =
!

On differentiating the above state, (w.r.t.) , we get

!
|
=
|

(2.92.)

(2.93.)

Also, from the time-dependent Schrodinger equation, we know,

!|!

!"

=
!|!
!"

!!

(2.94)

(2.95)

| = |
!

By comparing eqn. (2.93) and eqn. (2.95), we get the expression,

!!!
!"

= ! !

(2.96)

The above expression is a differential equation, which has the following solution,

!

! = ! (! ) !!! !

10

(2.96)