Chapter Two Matrix Formulation of Quantum Mechanics Matrix Representation of Operators
Chapter Two Matrix Formulation of Quantum Mechanics Matrix Representation of Operators
∧ ∧ ∧
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;
∧ ∧ ∧ ∧ ∧ ∧
i .i = j . j = k .k = 1 ≡ normalized
∧ ∧ ∧ ∧ ∧ ∧
i . j = j . k = k . i = ... = 0 ≡ orthogonal
Hence,
A.B = Ax .Bx + Ay By + Az Bz
Bx
= (Ax Ay Az ) By
B
z
Matrix of A Matrix of B
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
n
A = η1 A1 + η 2 A2 + η 3 A3 + ...... + η n An = ∑η i Ai
i =1
Where η1 ,η 2 ,....,η n are unit vectors (or basis) satisfying the relation;
ηn .ηm = δ 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;
1 0 0
0 1 0
η1 = 0 , η 2 = 0 ,……., η n = 0
. . .
0 0 1
In order to represent the wave functions and operators by matrices
we have to use the complete orthonormal eigen functions ϕi as a basis to
represent the wave function .i.e.
〈ϕ i | ϕ j 〉 = δ ij
n
ψ = c1ϕ1 + c2ϕ 2 + c3ϕ3 + ..... + cnϕ n = ∑ ciϕ i
i =1
n
U = b1ϕ1 + b2ϕ 2 + b3ϕ 3 + ...... + bnϕ n = ∑ biϕi
i =1
n m
〈ψ | U 〉 = ∑ ∑ ci*b j 〈ϕ i | ϕ j 〉
i =1 j =1
= ∑∑ c*i b jδ ij
i j
〈ψ | U 〉 = ∑ ci*bi
i
b1
b
= (c1* c*2 .... c*n ) 2
.
bn
Matrix of ψ Matrix of U
1 0 0
0 1 0
ϕ1 = 0 , ϕ 2 = 0 , ……, ϕ n = 0
. . .
0 0 1
∧
The operator A defined by;
∧
Aψ = U
∧
A ∑ ciϕ i = ∑ biϕi
i i
∑ c ϕ Aϕ
i
i
*
j i
= ∑ biϕ *jϕi
i
∧
∑ ci 〈ϕ j | A | ϕi 〉 = ∑ bi 〈ϕ j | ϕi 〉
i i
= ∑ biδ ji
i
∑ c ( A)
i
i ji = bj
= ∫ ϕi* Aϕ j dτ
∧
*
∧ *
= 〈ϕ i | A | ϕ j 〉 = Aij
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 ϕi are an eigen function of A . i.e.
∧
Aϕ i = aiϕ i
∧
( A )ji = 〈ϕ j \ Aϕi 〉 = ai 〈ϕ j \ ϕi 〉 = aiδ ji
∴ Aji = [ a j ,i = j
0 ,i ≠ j
∧
Then the matrix of A is diagonal
A11 0 0 .... 0
∧
0 A22 0 .... 0
∴ A=
.... .... .... .... ....
0 0 0 .... Ann
Matrix Element of the Angular Momentum
∧2
L Ylm = h 2 l( l + 1 )Ylm
∧2
( L )m′ ,m = h 2l( l + 1 )δ m′ ,m
= alδ m′ ,m
∧2 ∧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
∧2
0 al 0 .... 0
L = 0 0 al .... 0
.... .... .... .... ....
0 0 0 .... al
∧
For the z- component l z
∧
l z Ylm = mhYlm
∧
( l z )m′ ,m = mhδ 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 0 .... 0
lz = 0 0 m 2h .... 0
.... .... .... .... ....
0 m lh
0 0 ....
∧
Since the spherical harmonics Ylm is not an eigen function of l x
∧
and l y , the matrices of each of these operators can not be found directly
∧2 ∧
as in the 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 )lz
∧ ∧ ∧ ∧ ∧ ∧ ∧ ∧
= 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 )
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 .
Now let,
∧
l + Ylm = αYlm′
∧ ∧ ∧
So, l z ( l + Ylm ) = α l z Ylm′
= αm′hYlm′
But,
∧ ∧ ∧
l z ( l + Ylm ) = ( m + 1 )h( l + Ylm )
= ( m + 1 )hαYlm′
Then
( m + 1 )hαYlm′ = αm′hYlm′
⇒ m′ = m + 1
Hence;
∧
l + Ylm = αYlm+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 = α .............( 3 )
This means
∧
l − Ylm = αYlm−1
∧
So, one can say that the operator ( l − ) is a destructive operator when it is
operator on Ylm will turn it to Ylm−1 and the non-zero matrix element of
∧
( l − ) are;
∧
( l − )m−1,m = α ............( 4 )
Or equivalently;
∧ ∧
( l + )m ,m−1 = ( l − )m ,m+1 = α .............( 5b )
= ( l + )m ,m−1
∧ ∧ ∧ ∧ ∧
( l + l − )mm = ( l + )m ,m+1 .( l − )m−1,m ..........( 7 )
From equations (6) and (7) we have;
∧ 1
α = ( l + )m ,m−1 = h{( l + m )( l − m + 1 )} 2 ........( 8 a )
Or;
∧ 1
α = ( l − )m−1,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 lx
∧ ∧ ∧
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 ,m−1 and ( l − )m+1,m
∧
Thus the non-zero matrix elements of l x are;
∧
1 ∧ h 1
( l x )m ,m−1 = ( l + )m ,m−1 = {( l + m )( l − m + 1 )} 2
2 2
Or;
∧
1 ∧ h 1
H.w: ( l x )m−1,m = ( l − )m−1,m = {( l + m )( l − m + 1 )} 2
2 2
∧ ∧ ∧
l + − l − = 2i l y
∧ ∧ ∧
2i( l y )m ,m−1 = ( l + )m ,m−1 − ( l − )m ,m−1
∧
1 ∧
∴ ( l y )m ,m−1 = ( l + )m ,m−1 = α
2i
− ih 1
= {( l + m )( l − m + 1 )} 2
2
Or;
∧ ∧ ∧
2i( l y )m−1 ,m = ( l + )m−1,m − ( l − )m−1 ,m
∧
= −( l − )m−1,m = α
∧
ih 1
( l y )m−1,m = {( l + m )( l − m + 1 )} 2
2
∧ ∧
∴ ( l y )m ,m−1 = −( l y )m−1,m
III. Matrix Treatment:
d dA
I) for a system in a stationary state 〈 A〉 = 〈 〉
dt dt
Proof:
∧
〈 A〉 = ∫ψ (*r ,t ) Aψ ( r ,t ) dτ = ∫ψ (*r ,t ) Aψ ( r ,t ) dτ
i i
Et − Et
= ∫ψ (*r )e h Aψ ( r )e h
dτ
= ∫ψ (*r ) Aψ ( r )dτ
d dA
〈 A〉 = ∫ψ (*r ) ψ ( r )dτ
dt dt
= ∫ψ (*r ) A& ψ ( r ) dτ
∧
⋅
= ∫ψ (*r ) Aψ ( r ) dτ
= 〈 A& 〉
dA
=〈 〉
dt
∧
e.g. 〈 x〉 = ∫ψ (*x ,t ) xψ ( x ,t )dx
〈 x〉 = ∫ψ (*x ,t ) xψ ( x ,t ) dx
〈 x〉 = ∫ψ (*x ) xψ ( x ) dx
d
〈 x〉 = ∫ψ (*x ) x&ψ ( x ) dx
dt
∧
d .
〈 x〉 = ∫ψ (*x ) xψ ( x ) dx
dt
∧
dx
= ∫ψ (*x ) ( )ψ ( x ) dx
dt
dx
=〈 〉
dt
∧
II) 〈 A〉 = ∫ψ * Aψ dτ
∧
= ∑∑ c*n cm ∫ψ n* Aψ m dτ
n m
= ∑∑ c*n cm Anm ( t )
n m
= iωnm Anm ( t )
Now canceling the time factor the both sides we get;
i
A& nm = iωnm Anm = ( En − Em ) Anm
h
−
−& ∂V
By using the Ehrenfest's theorem p = − one may find the
∂x
equation of motion for the H.O. to be;
∧
.. ∧
x+ ω 2 x = 0
∧
.. ∧
∫ψ xψdx +ω ∫ψ xψdx = 0
* 2 *
∑∑ c
m n
*
c
m n
{∫ψ *
m
&x&ψ n dx + ω 2 ∫ψ m* xψ n dx} = 0
∑∑ c c {&x&
m n
*
m n mn
+ ω 2 xmn } = 0
⇒ &x&mn + ω 2 xmn = 0
But;
&x&mn = iωmn x& mn
= iωmn .( iωmn xmn )
2
= −ωmn xmn
2
∴ (ωmn − ω 2 ) xmn = 0
⇒ ωmn = mω
Then the only non-zero matrix elements are those for which ωmn = ω and
ωmn = −ω .
n+1
+ω n
−ω n −1
In matrix form;
( x&x )mn − ( xx& )mn = ( −ih / m )δ mn
Using the matrix multiplication rule;
( fg ) mn = ∑ f ml gln
l
We have;
∑ {x&ml xln − xml x&ln } = (−ih / m)δ mn
l
For m=n
i ∑ {ω nl xnl xln − xnlωln xln } = ( −ih / m )
l
In this sum only the terms with l = n m 1 are different from zero, so;
{ω x 2
n ,n −1 n ,n−1 + ωn ,n+1 xn2,n+1} = −h / 2 m
Q ωn ,n−1 = −ωn ,n+1 = +ω
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 / 2mω ]
And so;
− h ( n + 1 )h nh
xn2,n−1 = + =
2 mω 2 mω 2 mω
( n + 1 )h nh
∴ xn ,n+1 = xn+1,n = and xn ,n−1 = xn−1 ,n =
2 mω 2 mω
Now the energy eigen values can be found as follows;
∧ ∧ ∧
H = T +V( x )
∧ 2
∧2
1 . 1
= m x + mω x 2
2 2
In matrix form;
1 2 1
H mn = mx& mn + mω 2 xmn
2
2 2
1 1
= m( iωmn xmn )2 + mω 2 xmn
2
2 2
1
= m∑ {( i )2 ωml xml .ωln xln + ω 2 xml xln }
2 l
1
{
En = H nn = m∑ − ωnl xnl .ωln xln + ω 2 xnl xln , ωln = −ωnl
2 l
}
1
= m∑ {ωn2l + ω 2 }xn2l
2 l
1
{
= m (ωn2, n −1 + ω 2 ) xn2, n −1 + (ωn2, n +1 + ω 2 ) xn, n +1
2
}
1 nh ( n + 1)h
= m (ω 2 + ω 2 ). + ((−ω ) 2 + ω 2 ).
2 2mω 2mω
1 2 nh ( n + 1 )h
= m2ω . + 2ω 2 .
2 2mω 2mω
1 nhω ( n + 1 )hω
= m +
2 m m
1
= ( 2n + 1 )hω
2
1
∴ E n = h ω( n + ) where n=0, 1, 2, ……
2
In order to deduce the wave functions ψ n we can show that the only non-
∧
.
zero matrix elements of the operator ( x ± iωx ) are;
2nhω
H.W: ( x& − iωx )n−1,n = −( x& + iωx )n ,n−1 = −i
m
From this equation it can be realized that;
( x&ˆ − iωxˆ )ψ o = 0
∧
. ∧
∴ xψ o = iω xψ o
h dψ o
−i = iωxψ o
m dx
dψ o mω
= − x
ψo h
x
mω x
2
lnψ o ]ψ
ψ(x)
= −
(o)
h 2 0
⇒ ψ o ( x ) = ψ o ( 0 ) exp( − mωx 2 / 2h )
1
H.W: ψ o (0) = (mω / πh) 4
∧
. ∧
2 nhω
Since ( x + iω x )ψ n−1 = i ψn
m
⇒
m − ih d
ψn = + ωx ψ n−1
2 nhω mi dx
m h d
= − + ωx ψ n−1
2 nhω m dx
However by repeating the same procedure one may finally reach the
following recurrence formula;
1 2 mω
ψ n = ( mω / h / 2n n! π ) 2 e− mω x / 2h
Hn (x )
h
2 nhω
Problem: Show that; ( x& − iωx )n−1,n = −( x& + iωx )n ,n−1 = −i
m
∧
∧ . ∧
Solution: Assume that; f = x− iω x
In matrix form;
f mn = x&mn − iωxmn
= iωmn xmn − iωxmn
= i( ωmn − ω ) xmn
Since the only non-zero matrix elements of xmn are xnm1 ,n and thus
ωn−1,n = −ω . So;
f n−1,n = i( ωn−1,n − ω ) xn−1,n
nh 2 nωh
= −2iωxn−1,n = −2iω = −i
2 mω m
Similarly;
∧
∧ .
f = x + iωx
f nm = xnm + iωxnm = i( ωnm + ω )xnm
⇒
f n ,n−1 = i( ωn ,n−1 + ω ) xn ,n−1
nh 2ωnh
= 2iω =i
2 mω m
∧+
nh ∧
H.W: Given xn ,n−1 = and x&mn = iωmn xmn find the form of a and a .
2 mω
Spin Angular Momentum
Lˆ2Yl m (θ , ϕ ) = h 2l (l + 1)Yl m (θ , ϕ )
and
lˆzYl m (θ , ϕ ) = mhYl m (θ , ϕ )
In addition to the physical concept of the angular momentum one can set
up the following equations;
∧2
S α ms = h 2 s( s + 1)α ms
and,
S zα ms = mms hα ms
Where,
s = 12 and ms = ± 12
However, α1/2 and α-1/2 are spin wave functions for spin up and down
respectively. So,
∧2 Ŝ zα 1 = 12 hα 1
S α ± 1 = 34 h 2α ± 1 and 2 2
1 hα 1
2 2
Ŝ zα − 1 = − 2 −2
2
For simplicity one may assume α1/2 =α1 and α-1/2 =α2 . Hence,
i = 12
α= ∑ ci α i
i = − 12
α = c α + c− α −
1 1i 1 1i
2 2 2 2
α = c1α 1 + c 2α 2
2
I) Matrix of Ŝ
∧2 ∧2
According to, S α1 = h 2 s (s + 1)α1 and S α 2 = h 2 s( s + 1)α 2
One may built up the matrix of this operator to be;
∧2 ( Sˆ 2 )12 4 h 0 3 2 1 0
( Sˆ 2 ) 3 2
S = 2 11 = 3 h2
= 4h
( Sˆ ) 21 ( Sˆ 2 ) 22 0 4 0 1
II) Matrix of Ŝ z
∧ (Sˆ ) ( Sˆ z )12 12 h 0 1 1 0 1
S z = z 11 = 1 h 2 0 − 1 2
= h = hσˆ z
( Sˆ ) ( Sˆ ) 0 −
z 21 z 22 2
Now,
∧ α 1 0 α1 1 α1 1 α 1
S z 1 = 12 h = 2 h α = 2 h − α
α 2 0 − 1 α 2 2 2
III) Matrix of Ŝ x
Assume that;
∧ ∧
S x α 1 → α1′ and S x α 2 → α 2′
∧
α1′ = S x α1 = a11α1 + a12α 2
∧
α 2′ = S x α 2 = a11α1 + a12α 2
From equation;
∧
( S x )11 = a11δ 11 + a12δ 12 = a11
∧
( S x ) 21 = a11δ 21 + a12δ 22 = a12
While equation gives;
∧
( S x )12 = a 21δ 11 + a 22δ 12 = a 21
∧
( S x ) 22 = a 21δ 21 + a 22δ 22 = a 22
∧ (Sˆ ) ( Sˆ x )12 0 1 h
0 1 1
S x = x 11 =
2
= 12 h = 2 hσˆ x
ˆ ( Sˆ x ) 22 12 h 0 1 0
(S x ) 21
Now;
∧ α 0 1 α 1 1 α 2
S x 1 = 12 h = 2 h α
α 2 1 0 α 2 1
IV) Matrix of Ŝ y
∧
α1′ = S y α 1 = a11α1 + a12α 2
∧
α1′ = S y α 2 = a11α1 + a12α 2
Hence;
∧
( S y )11 = a11δ 11 + a12δ 12 = a11
∧
( S y ) 21 = a11δ 21 + a12δ 22 = a12
∧
( S y )12 = a 21δ 11 + a 22δ 12 = a 21
∧
( S y ) 22 = a 21δ 21 + a 22δ 22 = a 22
In accordance to relation;
∧ ∧ i 1
( l y ) m,m−1 = −(l x ) m−1,m = − h{(l + m)(l − m + 1)} 2
2
The following formula may set up;
∧ ∧ i 1 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,
Now;
∧ α 0 − i α1 i − α 2
S y 1 = 12 h = 2 h α
α 2 i 0 α 2 1