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Chapter Two
Matrix Formulation of Quantum Mechanics
2-1 Matrix Representation of Vectors
The vector A in three dimension can be represent as:

A = i Ax + j Ay + k Az

Where i , j and k are the unit vectors represent the magnitude of A in x,

y and z directions. So, these unit vectors are "BASIS" to represent the
vector. Also we know that;

normalized

i .i = j . j = k . k = 1

orthogonal

i . j = j .k = k .i = ... = 0

Hence,
A.B = Ax .Bx + Ay By + Az Bz

= (Ax

Ay

Matrix of A

Az )

Bx

By
B
z

Matrix of B

So, we can represent the vector in three dimensions by a column or a row

matrix. Similarly the BASIS can be done as follows;

1
0
0

i = 0 , j = 1 and k = 0
0
0
1

Where,

0
1



i . j = (1 0 0) 1 = 0 And i . i = (1 0 0) 0 = 1
0
0

In N dimension the vector A is represent as;

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n

A = 1 A1 + 2 A2 + 3 A3 + ...... + n An = i Ai
i =1

Where 1 , 2 ,...., n are unit vectors (or basis) satisfying the relation;

n . m = nm
Thus,

B1

B2

A.B = A1 B1 + A2 B2 + ..... + An Bn = A1 A2 A3 .... An B3

.
B
n
Matrix of A
Matrix of B
Also the basis can be put in the matrix form as follows;
0
1
0



1
0
0
1 = 0 , 2 = 0 , ., n = 0



.
.

.

0
0
1

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2-2 Matrix Representation of Wave Functions and Operators

In order to represent the wave functions (and then operators) by
matrices we have to use the complete orthonormal eigen functions i as a
basis to represent the wave function .i.e.
i | j = ij
n

= c11 + c2 2 + c33 + ..... + cn n = cii

i =1
n

U = b11 + b2 2 + b3 3 + ...... + bn n = bii

i =1

The overlap integral of and U is;

n

| U = ci*b j i | j
i =1 j =1

= ci* b j ij
i

| U = ci*bi
i

= c1* b1 + c*2b2 + ....... + c*n bn

= (c1*

c*2

b1

b
* 2
.... cn )
.

bn

Matrix of

Matrix of U

The basis in matrix form are;

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1
0
0



0
1
0
1 = 0 , 2 = 0 , , n = 0



.
.
.
0
0
1

The operator A defined by;

A = U

A cii = bii
i

c A
i

*
j

= bi *ji

ci j | A | i = bi j | i
i

= bi ji
i

c ( A)
i

ji

= bj

Where j = 1,2 ,3 ,.....,n

Note: we must remember that most of the operators in Q.M. are
hermetion because it represents a real physical quantity (Why?).
i.e. Aji = Aij*

Proof: A ji = j | A | i

= *j Ai d

= i ( A j )* d
*

= i* A j d

*
= i | A | j = Aij

For j=1

c1 A11 + c2 A12 + .... + cn A1n = b1

j=2

c1 A21 + c2 A22 + .... + cn A2 n = b2

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c1 A31 + c2 A32 + .... + cn A3 n = b3

c1 An 1 + c2 An 2 + .... + cn Ann = bn
In matrix form;
A11 A12 .... A1n c1 b1

A
A
....
A
21
b2
22
2 n c2
=
.... ..... .... .... . .

A
A
....
A
n1
n2
nn cn
bn
j=3

Matrix
of

Matrix of A

Matrix
of U

Where each element Aji is called matrix element. The set of quantities

Aji with all possible j and i values is called matrix of A (or matrix of the
quantity A), and each of Aji is called the matrix element which
corresponds to the transition from state i to state j. Now if the basis i

are an eigen function of A . i.e.

Ai = aii

( A )ji = j \ Ai = ai j \ i = ai ji

Aji =

a j ,i = j

0 ,i j

Then the matrix of A is diagonal

A11

0
A=
....

0
A22

0
0

....
....

....

.... ....

....

0
....

Ann

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2-3 Matrix Treatment Of Linear Harmonic Oscillator

Before going in details one have to realize the following;

I) for a system in a stationary state

d
dA
A =
dt
dt

Proof:

A = (*r ,t ) A ( r ,t ) d = (*r ,t ) A ( r ,t ) d

i
Et
*
h
e
(r )

A ( r )

i
Et
h
e
d

= (*r ) A ( r ) d
d
dA
A = (*r ) ( r ) d
dt
dt
* &
= A d

(r )

(r )

= (*r ) A ( r ) d
= A&
dA
=
dt

e.g.

x = (* x ,t ) x ( x ,t ) dx
x = (* x ,t ) x ( x ,t ) dx
x = (* x ) x ( x ) dx
d
x = (*x ) x& ( x ) dx
dt

.
d
x = (* x ) x ( x ) dx
dt

= (* x ) (
=

dx
) ( x ) dx
dt

dx

dt

II) A = * A d

= c*n c m n* A m d
n m

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= c*n c m Anm ( t )
n m

These set of quantities Anm ( t ) with all possible n and m values is

called matrix of A quantity, and each of Anm ( t ) is called the matrix
element corresponding to the transition from state m to state n.
Since;

n ( r ,t ) = n ( r

i
Et
).e h

Thus;

Anm ( t ) = Anm

i
( E n E m )t
h
e

= Anm e i nmt

Where nm = ( E n E m ) / h is the transition frequency between state n

to and m.
d
( Anm ( t )) = A& nm ( t )
dt

= i nm Anm e i nmt
= i nm Anm ( t )
Now canceling the time factor the both sides we get;
i
A& nm = i nm Anm = ( E n E m ) Anm
h

&

By using the Ehrenfest's theorem p =

equation of motion for the H.O. to be;

..

x+ 2 x = 0

..

*
2
*
xdx + xdx = 0

*
m n

c c {&x&
*
m n

mn

*
m

&x& n dx + 2 m* x n dx} = 0

+ 2 xmn } = 0

&x&mn + 2 xmn = 0

But;
&x&mn = i mn x& mn

= i mn .( i mn x mn )
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V
one may find the
x

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2
= mn
xmn

2
(mn
2 ) xmn = 0

mn = m

Then the only non-zero matrix elements are those for which mn = and

mn = .
If we number all the stationary states so that the frequencies m
correspond to transitions n n m 1. i.e. mn = n m1, n = m. then the only
non-zero matrix elements are xn ,nm1 .
n+1

n
n1

Suppose that the wave functions are taken to be real, so;

xmn = m* x n dx = m* x n dx

= n ( x m )* dx = n* x m dx

xmn = xnm
This means that the matrix xmn is symmetrical.
In order to calculate the matrix elements xmn we may use the
following commutation rule;

p , x = ih
x

x x x x = ih / m
In matrix form;
( x&x )mn ( xx& )mn = ( ih / m ) mn
Using the matrix multiplication rule;
( fg )mn = f ml g ln
l

We have;
{x&ml xln xml x&ln } = (ih / m) mn
l

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i {ml xml xln xmlln xln } = ( ih / m) mn

l

For m=n
i {nl xnl xln xnlln xln } = ( ih / m )
l

Since xnl = xln and nl = ln

Then
2i {nl xn2l } = ( ih / m )
l

In this sum only the terms with l = n m 1 are different from zero, so;

2
n ,n 1 x n ,n 1

+ n ,n +1 xn2,n+1 = h / 2m

Q n ,n1 = n ,n+1 = +
xn2,n1 xn2,n+1 = h / 2m

..........( 1 )

Let n=0 be the number of the lowest state, so x0 ,1 must be zero. Thus
application of equation (1) will lead to;

xn2,n+1 = [( n + 1 )h / 2m ]
And so;
h ( n + 1 )h
nh
+
=
2 m
2 m
2 m
( n + 1 )h
nh
xn ,n+1 = xn+1 ,n =
and xn ,n1 = xn1 ,n =
2m
2m
Now the energy eigen values can be found as follows;
xn2,n1 =

H = T +V( x )

2
1 . 1
2
= m x + m x
2
2
In matrix form;
1 2 1
2
H mn = mx&mn
+ m 2 xmn
2
2
1
1
2
= m( imn xmn )2 + m 2 xmn
2
2
1
= m {( i )2 ml xml .ln xln + 2 xml xln }
2 l
1
En = H nn = m nl xnl .ln xln + 2 xnl xln , ln = nl
2 l

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1
m {n2l + 2 }xn2l
2 l
1
= m (n2, n 1 + 2 ) xn2, n 1 + (n2, n +1 + 2 ) xn , n +1
2
1
nh
( n + 1)h
= m( 2 + 2 ).
+ (( ) 2 + 2 ).

2
2m
2m
1
nh
( n + 1 )h
= m2 2 .
+ 2 2 .

2
2m
2m
1 nh ( n + 1 )h
= m
+

2 m
m

1
= ( 2n + 1 )h
2
1
where n=0, 1, 2,
E n = h ( n + )
2
=

In order to deduce the wave functions n we can show that the only non

zero matrix elements of the operator ( x ix ) are;

H.W: ( x& ix )n1 ,n = ( x& + ix )n ,n1 = i

From this equation it can be realized that;

( x& ix ) o = 0

x o = i x o

h d o
= ix o
m dx
d o
m
=
x
o
h

2
m x
ln o ] =

h 2 0
o ( x ) = o ( 0 ) exp( mx 2 / 2h )

( x)
(o)

H.W: o (0) = (m / h)

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2 n h
m

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2 nh
n
m

Since ( x + i x ) n1 = i

m ih d

+ x n1

2 nh mi dx

n =

m h d

+ x n1
2 nh m dx

However by repeating the same procedure one may finally reach the
following recurrence formula;
1

n = ( m / h / 2n n! ) 2 e m x

/ 2h

Hn (x

m
)
h

Problem: Show that; ( x& ix )n1 ,n = ( x& + ix )n ,n1 = i

2 n h
m

Solution: Assume that; f = x i x

In matrix form;
f mn = x&mn ixmn
= imn xmn ixmn
= i( mn ) xmn

Since the only non-zero matrix elements of xmn are xnm1,n and thus

n1 ,n = . So;
f n1,n = i( n1 ,n )xn1,n
= 2ixn1,n = 2i

nh
2 nh
= i
2 m
m

Similarly;

f = x + ix
f nm = xnm + ixnm = i( nm + ) xnm

f n ,n1 = i( n ,n1 + ) xn ,n1

= 2i

nh
2nh
=i
2 m
m
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+
nh
and x&mn = imn xmn find the form of a and a .
2 m

H.W: Given xn ,n1 =

2-4 Matrix Treatment of The Radial Angular Momentum

According to H-like atoms manipulation, it is seen that;
2

L Ylm = h 2 l( l + 1 )Ylm

So,
2

( L )m ,m = h 2 l( l + 1 ) m ,m
= al m ,m
2

Then the only non- zero matrix elements of ( L ) are ( L )m ,m which

equal to h 2 l( l + 1 ) where l = 0 ,1,2 ,...., n 1 and m = 0 ,m1,m2 ,.....,ml
al 0 0

0 al 0
2
L = 0 0 al

.... .... ....

0 0 0

0
0

....
al

....
....
....
....
....

For the z- component l z

l z Ylm = mhYlm

( l z )m ,m = mh m ,m

Then the non- zero matrix element of ( l z ) are ( l )m ,m which equal to mh ,

where m = 0 ,m1,m2 ,.....,ml
0
0
0

0
0 mh

lz = 0
0 m 2h

.... .... ....

0
0
0

....
....
....
....
....

0
0

....
m lh
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Since the spherical harmonics Ylm is not an eigen function of l x and l y ,

the matrices of each of these operators cannot be found directly as in the
2

case for L and l z . However, to do that we have to define the following

operators;

l + = l x + i l y and l = l x i l y

Now;
l z ,l + = l z l + l + l z

= l z ( l x + i l y ) ( l x + i l y )l z

= l z l x l x l z + i (l z l y l y l z )

= ih l y + i( ih l x )

= h( l x + i l y )

l z ,l + = h l +
..............( 1 )

H.w: l z ,l = h l ..........( 2 )

From equation (1)

l z l+ = h l+ + l+ l z

l z l + Ylm = h l + Ylm + l + l z Ylm

= h( l + Ylm ) + mh( l + Ylm )

= h( m + 1 )( l + Ylm )

It is seen that the function ( l + Ylm ) is an eigen function of the operator

( l z ) with an eigen value ( m + 1 )h .

Similarly one can find that;

l z ( l Ylm ) = ( m 1 )h( l Ylm )

Where the function ( l Ylm ) is an eigen function of the operator ( l z ) with

an eigen value ( m 1 )h .

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Now let,

l + Ylm = Ylm

So, l z ( l + Ylm ) = l z Ylm

= mhYlm
But,

l z ( l + Ylm ) = ( m + 1 )h( l + Ylm )

= ( m + 1 )hYlm
Then
( m + 1 )hYlm = mhYlm
m = m + 1
Hence;

l + Ylm = Ylm+1

This means that ( l + ) is a creative operator since it turns Ylm to Ylm+1 .

therefore the non-zero matrix elements of l + are;

( l + )m+1,m =

.............( 3 )

In a similar procedure if it is assumed that;

l Ylm = Ylm

So, l z ( l Ylm ) = l z Ylm

= mhYlm
But,

l z ( l Ylm ) = ( m 1 )h( l Ylm )

= ( m 1 )hYlm
Then
mhYlm = ( m 1 )hYlm
m = m 1
This means

l Ylm = Ylm1
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So, one can say that the operator ( l ) is a destructive operator when it is
operator on Ylm will turn it to Ylm1 and the non-zero matrix element of

( l ) are;

( l )m1 ,m =

............( 4 )

From equation (3) and (4) we find;

( l + )m+1 ,m = ( l )m1,m =

.............( 5a )

Or equivalently;

( l + )m ,m1 = ( l )m ,m+1 =

.............( 5b )

In order to find we have to follow the following procedure;

l + l = ( l x + i l y )( l x i l y )
2

= lx + l y i lx l y + i l y lx
2

= l x + l y + i( l y l x l x l y )
2

= L l2 z + h l z
Now;

l + l \ lm = L \ lm l z \ lm + h l z \ lm

= h 2 l(l + 1) h 2 m 2 + h 2 m | lm

lm | l + l | lm = h 2 l(l + 1) m 2 + m l l m m

( l + l )mm = h 2 ( l + m )( l m + 1 )

.............( 6 )

From the definition of matrix multiplication we have;

( l + l )mm = ( l + )mn ( l )nm

n

From equation (5) we find; ( l + )m+1 ,m = ( l )m1,m =

(l + l ) mm = (l + ) m +1, m .(l ) m 1, m = (l + ) m, m 1

From equations (6) and (7) we have;

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..........( 7 )

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= ( l + )m ,m1 = h{( l + m )( l m + 1 )} 2

Quantum Mechanics/M.Sc. Course

........( 8 a )

Or;

= ( l )m1 ,m = h{( l + m )( l m + 1 )} 2

........( 8b )

Now we can find the matrix elements of ( l x ) and ( l y ) as follows;

l+ + l = 2 l x

2 l x Ylm 1 = l + Ylm 1 + l Ylm 1

2( l x ) m, m 1 = (l + ) m, m 1 + (l ) m, m 1

It had been found that the non-zero matrix elements of ( l + ) and ( l ) are
those;

( l + )m ,m1 and ( l )m+1 ,m

Thus the non-zero matrix elements of l x are;

1
1
h
( l x )m ,m1 = ( l + )m ,m1 = {( l + m )( l m + 1 )} 2
2
2
Or;

1
1
h
H.w: ( l x )m1 ,m = ( l )m1,m = {( l + m )( l m + 1 )} 2
2
2

l + l = 2i l y

2i( l y )m ,m1 = ( l + )m ,m1 ( l )m ,m1

1
( l + )m ,m1 =
2i
1
ih
{( l + m )( l m + 1 )} 2
=
2

( l y )m ,m1 =

Or;

2i( l y )m1,m = ( l + )m1,m ( l )m1,m

= ( l )m1 ,m =

( l y )m1 ,m =

1
ih
{( l + m )( l m + 1 )} 2
2

( l y )m ,m1 = ( l y )m1,m
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2-5 Matrix Treatment of The Spin Angular Momentum

Indeed analytical investigation of spin angular momentum is an
advanced problem in Q.M. and required to start from Dirac's equation
rather than S.E.. But, by making use a simple comparison between orbital
and its counterpart spin angular momentum one may reach a considerable
results. In accordance to equations;
L2Yl m ( , ) = h 2l (l + 1)Yl m ( , )

and
l Y m ( , ) = mhY m ( , )
z l

In addition to the physical concept of the angular momentum one can set
up the following equations;
2

S ms = h 2 s (s + 1) ms
and,

S z ms = mms h ms
Where,

s = 12

ms = 12

and

However, 1/2 and -1/2 are spin wave functions for spin up and down
respectively. So,
2

S 1 = 34 h 2 1
2

and

S z 1 = 12 h 1
2

S z 1 = 12 h 1
2

For simplicity one may assume 1/2 =1 and -1/2 =2 . Hence,

i = 12

ci i

i = 12

= c + c
1
2

1i
2

1
2

1i
2

= c11 + c 2 2
2
I) Matrix of S

According to,

S 1 = h 2 s( s + 1) 1

and

S 2 = h 2 s ( s + 1) 2

One may built up the matrix of this operator to be;

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( S 2 )11 ( S 2 )12 34 h 2
S = 2
=
2
( S ) 21 ( S ) 22 0

Quantum Mechanics/M.Sc. Course

0 3 2 1 0
= 4h

3 h2

0 1
4

II) Matrix of S z
Similarly, with aid of equations,

S z 1 = 12 h 1

and

S z 2 = 12 h 2

Matrix of this operator can be built as in the form;

( S )
0 1 1 0 1
( S z )12 12 h
S z = z 11
= h z
=
= h

1 2 0 1 2

( S z ) 21 ( S z ) 22 0 2 h

Now,

1 0 1 1 1 1 1
S z 1 = 12 h
= 2 h = 2 h
0 1 2
2
2
2

III) Matrix of S x
Assume that;

S x 1 1

and

S x 2 2

Which can be given as a linear superposition in terms of spin up and spin

down wave functions as follows;

1 = S x 1 = a111 + a12 2

2 = S x 2 = a111 + a12 2
From the first of these equations one can get;

( S x )11 = a11 11 + a12 12 = a11

( S x ) 21 = a11 21 + a12 22 = a12

While from the second one obtain;

( S x )12 = a 21 11 + a 22 12 = a 21

( S x ) 22 = a 21 21 + a 22 22 = a 22

Regarding angular momentum investigation. i.e.

(l x ) m1,m = (l x ) m,m1 =

1
h
{(l + m)(l m + 1)} 2
2

The following formula may set up;

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( S x ) ms 1,ms = ( S x ) ms ,ms 1 =

2014-2015

Quantum Mechanics/M.Sc. Course

h
{(s + m s )(s m s + 1)}12 = h
2
2

Therefore, the only non-zero matrix element of the x-component of spin

angular momentum are those for ms=1/2. i.e.

(S x ) 1,1

2 2

and ( S x ) 1 , 1
2

Which equal to . Then,

( S )
S x = x 11

( S x ) 21

( S x )12 0
=
( S x ) 22 12 h

h 1 0 1 1
= h x
= h
0 2 1 0 2

1
2

Now;

0 1 1 1 2
S x 1 = 12 h
= 2 h
1 0 2
2
1

IV) Matrix of S y
Following a similar procedure one may get the y-component matrix of
spin angular momentum. Again assume that;

S y 1 1

and

S y 2 2

Which can be given as a linear superposition in terms of 1 and 2 as

follows;

1 = S y 1 = a11 1 + a12 2

1 = S y 2 = a11 1 + a12 2

Hence;

( S y )11 = a11 11 + a12 12 = a11

( S y ) 21 = a11 21 + a12 22 = a12

( S y )12 = a 21 11 + a 22 12 = a 21

( S y ) 22 = a 21 21 + a 22 22 = a 22

In accordance to the relation;

1
i
(l y ) m,m 1 = ( l x ) m 1,m = h{(l + m)(l m + 1)} 2
2

The following formula may set up;

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1
i
i
( S x ) ms ,m 1s = ( S x ) ms 1,ms = h{( s + m s )( s m s + 1)} 2 = h
2
2

Therefore, the only non-zero matrix element of the y-component of spin

angular momentum are those for ms=1/2. i.e.

i
(S y ) 1 , 1 = - (S y ) 1 , 1 = h
2
2
2
2
2

Then,

( S )
S y = y 11
( S y ) 21

( S y )12 0
=
( S y ) 22 2i h

h 1 0 i 1
= h y
= h
0 2 i 0 2

i
2

Now;

0 i 1 i 2
S y 1 = 12 h
= 2 h
i 0 2
1
2

The matrices x, y, z called Pauli's Spin Matrices.

H.W.:
1) Prove that;
i- S z = 21 h(c1* c1 - c*2 c2 ) z = (c*1 c1 - c*2 c2 ) .
ii- S x = 21 h(c1* c2 - c*2 c1 ) z = (c*1 c2 - c*2 c1 ) .
iii- S y = 12 h(c1* c2 - c*2 c1 ) z = (c*1 c2 - c*2 c1 ) .
2) For the probability of spin up equal to that of spin down evaluate each
of the relation in (1).

3) Evaluate the following commutation relation; [ z , x ], x , y and

, z .

4) Set up the matrices of the operators S + and S where S + = S x + iS y and

S = S x iS y .

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